An anthracene compound, a preparation method and application thereof

Abstract

The present application relates to the technical field of organic electroluminescence device display, in particular to an anthracene compound, a preparation method and application thereof. The anthracene compound provided by the present application contains an electron transport unit of benzimidazole, can promote electron injection and transport in the light-emitting layer of the device, promote the charge transport balance of holes and electrons, and reduce the driving voltage. By introducing a steric hindrance group at the ortho position of the benzimidazole electron transport unit, the torsion angle of the anthracene unit and the benzimidazole is increased, thereby reducing the conjugation degree of the two, avoiding the electron-withdrawing effect of the benzimidazole from changing the excited state characteristics of the anthracene unit, ensuring the efficient triplet exciton upconversion property thereof, and ensuring the high exciton utilization rate and blue light emission of the anthryl group. Meanwhile, the benzimidazole as an excellent electron transport unit can effectively improve the electron transport capacity of the host and promote the charge transport balance of the electroluminescence device. The electroluminescence device obtained in the end exhibits high luminous efficiency and low driving voltage.

Description

Technical Field

[0001] This invention relates to the field of organic electroluminescent device display technology, specifically to an anthracene compound, its preparation method, and its application. Background Technology

[0002] Organic light-emitting diodes (OLEDs) are devices that convert electrical energy into light energy. They have advantages such as high efficiency, high contrast, fast response speed, and flexibility, and are a new generation of display technology. Their device structure typically consists of an anode, a hole injection layer, a hole transport layer, an electron blocking layer, an emissive layer, a hole blocking layer, an electron transport layer, an electron injection layer, and a cathode. Its light-emitting principle is as follows: holes are injected from the anode and enter the emissive layer through the hole injection layer, the hole transport layer, and the electron blocking layer. At the same time, electrons are injected from the cathode and enter the emissive layer through the electron injection layer, the electron transport layer, and the hole blocking layer. Then, holes and electrons recombine in the emissive layer to form 25% singlet excitons and 75% triplet excitons. Singlet excitons can directly emit light, while triplet excitons, due to spin inversion forbidden restrictions, cannot directly emit light.

[0003] Blue OLED devices have consistently suffered from poor performance, directly limiting the display effect of OLED panels. The key functional layer determining the performance of OLED devices is the emissive layer, which is typically composed of a host and a dye. The host's functions include injecting charge, transporting charge, generating excitons, and converting excitons. Therefore, the host's energy level structure, transport characteristics, and excited-state behavior play a decisive role in the performance of OLED devices. Blue OLED devices commonly use triplet-triplet annihilation (TTA) type hosts. Their key feature is the ability to convert two non-emissive triplet excitons into one emissive singlet exciton, thus utilizing the radiation-forbidden triplet exciton. Simultaneously, it has the advantage of low triplet energy levels, effectively avoiding the generation of high-energy excited states that could damage the device.

[0004] Currently, the commonly used TTA-type host is anthracene derivative, which has two problems: First, most anthracene TTA hosts have excessively high hole transport mobility and poor electron transport capability, resulting in an imbalance in carrier transport. Second, in order to improve the carrier transport characteristics of anthracene materials, it is usually necessary to introduce groups with electron-donating or electron-withdrawing properties. However, the introduction of these groups will change the energy level structure and excited state characteristics of anthracene itself, which will seriously affect the ability of the TTA host to convert and utilize triplet excitons. These two reasons directly lead to a decrease in the efficiency of blue light devices and an increase in driving voltage. Summary of the Invention

[0005] In view of this, the technical problem to be solved by the present invention is to provide an anthracene compound, its preparation method and application. The anthracene compound provided by the present invention is used as the main material of a blue electroluminescent device, and the resulting electroluminescent device has high luminous efficiency and low driving voltage.

[0006] This invention provides an anthracene compound having the structure of Formula 1:

[0007]

[0008] Wherein, x and y are independently 1 or 2;

[0009] The z is 0 or 1;

[0010] Ar1 and Ar2 independently include C6 to C6. 60 aryl;

[0011] Ar5 and Ar6 independently include C6 to C6. 60 aryl or C3~C 29 heteroaryl groups;

[0012] R1 and R3 independently include C1 to C2. 10 Alkyl groups, C6-C 60 aryl, C6-C 60 Deuterated aryl, C3~C 60 heteroaryl or C3-C 60 Deuterated heteroaryl groups;

[0013] The R1 is located at the ortho position of all Ar6-substituted benzimidazole groups attached to the Ar1;

[0014] The R3 is located at the ortho position of all Ar5-substituted benzimidazole groups attached to the Ar2.

[0015] The anthracene compound provided by this invention has the structure of Formula 1, which is based on an anthracene group as the main structural component. Two unfused carbon atoms on the central benzene ring are respectively connected to Ar1 and Ar2 groups. The Ar1 group is connected to an R1 group and an Ar6-substituted benzimidazole group, and the Ar2 group is connected to an R3 group and an Ar5-substituted benzimidazole group. In this invention, z is 0 or 1. When z is 0, R3 is directly connected to the anthracene group in Formula 1, while Ar2 and its connected Ar5-substituted benzimidazole group are absent.

[0016] In this invention, the Ar1 group is connected to an R1 group and an Ar6-substituted benzimidazole group, where y represents the number of Ar6-substituted benzimidazole groups connected to the Ar1 group, and y is 1 or 2. Specifically, when y is 2, the two Ar6-substituted benzimidazole groups connected to the Ar1 group can be the same or different.

[0017] In this invention, the Ar2 group is connected to an R3 group and an Ar5-substituted benzimidazole group; the x represents the number of Ar5-substituted benzimidazole groups connected to the Ar2 group, and x is 1 or 2. In particular, when x is 2, the two Ar5-substituted benzimidazole groups connected to the Ar2 group can be the same or different.

[0018] R1 and R3 in this invention independently include C1 to C 10 Alkyl groups, C6-C 60 aryl, C6-C 60 Deuterated aryl, C3~C 60 heteroaryl or C3-C 60 Deuterated heteroaryl groups.

[0019] Preferably, R1 and R3 independently comprise C1-C5 alkyl, phenyl, deuterated phenyl, cyano-substituted phenyl, cyano-substituted deuterated phenyl, C6-C5 alkyl, phenyl, ... C6-C5 10 Aryl-substituted phenyl, deuterated C6-C 10 Aryl-substituted phenyl, naphthyl, deuterated naphthyl, C6-C 10 Aryl-substituted naphthyl groups, deuterated C6-C6 groups 10 Aryl-substituted naphthyl, biphenyl, deuterated biphenyl, C6-C 10 Aryl-substituted biphenyl, deuterated C6-C 10 Aryl-substituted biphenyl, anthracene, deuterated anthracene, C6-C 10 Aryl-substituted anthracene, deuterated C6-C 10 Aryl-substituted anthracene, phenanthrene, deuterated phenanthrene, C6-C 10 Aryl-substituted phenyl groups, deuterated C6-C 10 aryl-substituted phenyl groups, C3-C 16 heteroaryl or C3~C 16 Deuterated aromatic compounds.

[0020] More preferably, R1 and R3 independently include one of the groups having the structure of formula R-1 to formula R-48;

[0021]

[0022]

[0023] Wherein, D is a deuterium atom that replaces the hydrogen atom on the aryl group attached thereto, n represents the number of substitutions, and n is an integer from 0 to 13. This indicates that the bond can be attached to a suitable atom on other groups.

[0024] Wherein, the D n The H atom on the benzene ring of each group having the structure of formula R-4 to R-6, R-9 to R-10, R-25 to R-44 is replaced by n deuterium atoms, where n is an integer from 0 to 13, and the number of n does not exceed the number of H atoms on the benzene ring of each group having the structure of formula R-4 to R-6, R-9 to R-10, R-25 to R-44. Non-limiting examples include groups having the structure of formula R-4-a or groups having the structure of formula R-5-a;

[0025]

[0026] in, This indicates that the bond can be attached to a suitable atom on other groups.

[0027] In this invention, R1 is located adjacent to all Ar6-substituted benzimidazole groups attached to Ar1; R3 is located adjacent to all Ar5-substituted benzimidazole groups attached to Ar2. Specifically, when there is only one Ar6-substituted benzimidazole group attached to Ar1, R1 is connected to any one of the two carbons adjacent to the carbon with the Ar6-substituted benzimidazole group attached to Ar1; when there are two Ar6-substituted benzimidazole groups attached to Ar1, these two Ar6-substituted benzimidazole groups must be meta-positions, and R1 is connected to the carbon with the common adjacent position of the carbons with the two Ar6-substituted benzimidazole groups attached to Ar1. The positional relationship between R3 and all Ar5-substituted benzimidazole groups attached to Ar2 is similar and will not be repeated.

[0028] The Ar5 and Ar6 described in this invention independently include C6 to C. 60 aryl or C3~C 29 The heteroaryl group. Preferably, Ar5 and Ar6 independently comprise C6 to C6. 12 aryl or C3~C 11 More preferably, Ar5 and Ar6 independently comprise phenyl, naphthyl, biphenyl, cyano-substituted phenyl, trifluoromethyl-substituted phenyl, or azaaryl. In some embodiments of the invention, Ar5 and Ar6 independently comprise one of a group having a structure of formula a-1 to a-25:

[0029]

[0030] in, This indicates that the bond can be attached to a suitable atom on other groups.

[0031] The Ar1 and Ar2 described in this invention independently include C6 to C. 60 The aryl group. Preferably, Ar1 and Ar2 independently comprise C6 to C6. 31 The aryl group. More preferably, when y is 1, the Ar1 includes a group having the structure of formula 2; when y is 2, the Ar1 includes a group having the structure of formula 3;

[0032]

[0033] Wherein, q is 0 or 1;

[0034] The Ar3 includes C6 to C6. 54 The aryl group preferably includes C6 to C6. 25 The aryl group, more preferably including phenyl, naphthyl, anthraceneyl, phenanthryl, biphenyl, fluorenyl or spirodifluorenyl;

[0035] When x is 1, Ar2 includes a group having the structure of Formula 4; when x is 2, Ar2 includes a group having the structure of Formula 5.

[0036]

[0037] Wherein, p is 0 or 1;

[0038] The Ar4 includes C6 to C6. 54 The aryl group preferably includes C6 to C6. 25 The aryl group, more preferably including phenyl, naphthyl, anthraceneyl, phenanthryl, biphenyl, fluorenyl or spirodifluorenyl;

[0039] in, This indicates that the bond can be attached to a suitable atom on other groups.

[0040] In this invention, for the Ar1 group, when y in Formula 1 is 1, the Ar1 group includes a group having the structure of Formula 2. Since R1 in Formula 1 of this invention is located ortho to all Ar6-substituted benzimidazole groups attached to Ar1, the two groups drawn from the benzene ring in Formula 2... It must be connected to the two adjacent carbons on the benzene ring of Formula 2 and to the R1 group and the Ar6-substituted benzimazole group in Formula 1, respectively, while the one drawn from Ar3... It then attaches to the anthracene main structural group in Formula 1. Non-limiting examples include groups with the structure shown in Formula 2-a:

[0041]

[0042] When y is 2 in Formula 1, the Ar1 group includes a group having the structure of Formula 3. Since R1 in Formula 1 of this invention is located ortho to all Ar6-substituted benzimidazole groups attached to Ar1, the three groups drawn from the benzene ring in Formula 3... There must be two carbons that are meta-positioned on the benzene ring of Formula 3 and are also connected to the Ar6-substituted benzimidazole group in Formula 1. The remaining carbon is connected to the carbon in the common ortho position of the two carbons and is also connected to the R1 group in Formula 1. Non-limiting examples include groups with the structure shown in Formula 2-b:

[0043]

[0044] In this invention, when the Ar1 group includes a group having the structure of Formula 2 and q is 0, the Ar1 group is a group having the structure of Formula 2-c. When the Ar1 group includes a group having the structure of Formula 3 and q is 0, the Ar1 group is a group having the structure of Formula 2-d.

[0045]

[0046] When the Ar1 group is a group having the structure of formula 2-c, since R1 in formula 1 of the present invention is located ortho to all Ar6-substituted benzimidazole groups attached to Ar1, the three groups drawn from the benzene ring in formula 2-c are... There must be two carbons adjacent to each other on the benzene ring, which are respectively attached to the R1 group and the Ar6-substituted benzimazole group in Formula 1, and the remaining carbon is attached to any remaining carbon on the benzene ring and to the anthracene main structural group in Formula 1. Non-limiting examples include groups having the structure of Formula 2-e;

[0047]

[0048] When the Ar1 group is a group having the structure of Formula 2-d, since R1 in Formula 1 of the present invention is located ortho to all Ar6-substituted benzimidazole groups attached to Ar1, the four groups drawn from the benzene ring in Formula 2-c are... Two of the carbon atoms must be attached to the two meta-position carbons on the benzene ring and to the Ar6-substituted benzimazole group in Formula 1; one carbon atom is attached to the common ortho-position carbon of the two meta-position carbons and to the R1 group in Formula 1; and the remaining carbon atom is attached to any of the remaining carbon atoms on the benzene ring and to the anthracene main structural group in Formula 1. Non-limiting examples include groups having the structure of Formula 2-f.

[0049]

[0050] In this invention, the Ar2 group is treated similarly to the Ar1 group described above, and will not be repeated here.

[0051] In some embodiments of the present invention, Ar1 and Ar2 independently include one of the groups having the structures shown in Formula A-1 to Formula A-32;

[0052]

[0053] In some embodiments of the present invention, the anthracene compounds provided by the present invention have one of the structures of formula H-1 to formula H-195;

[0054]

[0055]

[0056]

[0057]

[0058]

[0059]

[0060]

[0061]

[0062]

[0063]

[0064]

[0065]

[0066]

[0067]

[0068]

[0069] This invention also provides a method for preparing anthracene compounds according to any of the above-described technical solutions, comprising the following steps:

[0070] S1) Reacting a compound having the structure of Formula 6 with a compound having the structure of Formula 7 yields a compound having the structure of Formula 7.

[0071] Compounds with the structure of Formula 8;

[0072]

[0073] Wherein, X1 and X2 independently include Cl or Br; Ar1, Ar6, R1 and y are the same as above, and will not be repeated here;

[0074] S2) The compound having the structure of Formula 8 from step S1) is boronized and then reacted with the compound having the structure of Formula 9 to obtain the anthracene compound;

[0075]

[0076] X3 includes Cl or Br; Ar2, Ar5, R3 and x are the same as described above and will not be repeated.

[0077] This invention first reacts a compound having a structure of formula 6 with a compound having a structure of formula 7 to obtain a compound having a structure of formula 8. Specifically, this invention reacts a compound having a structure of formula 6 and a compound having a structure of formula 7 in a solvent at a 1:1 molar ratio to obtain a compound having a structure of formula 8; the solvent is not particularly limited, and may include, for example, anisole.

[0078] After obtaining a compound having the Formula 8 structure, the present invention borates the compound having the Formula 8 structure. Specifically, under a protective gas atmosphere, the compound having the Formula 8 structure is reacted with a borate reagent, a co-catalyst, and a palladium catalyst in a solvent to borate the compound having the Formula 8 structure; the reaction temperature is 60–110°C; and the reaction time is 10–15 h. In some embodiments of the present invention, the molar ratio of the compound having the Formula 8 structure to the borate reagent, co-catalyst, and palladium catalyst is (7–20):35:35:0.7. In some embodiments of the present invention, the borate reagent includes at least one of pinacol diborate, neopentyl glycol diborate, and bis(catechol)borate; the co-catalyst includes at least one of potassium acetate, potassium carbonate, sodium carbonate, and potassium phosphate; the palladium catalyst includes at least one of Pd(dppf)Cl2, Pd(dtbpf)Cl2, and Pd-132; and the solvent includes at least one of dioxane and toluene.

[0079] This invention involves boronizing the compound having the structure of Formula 8, and then reacting the resulting product with a compound having the structure of Formula 9 to obtain the anthracene compound. Specifically, the product obtained after boronizing the compound having the structure of Formula 8, the compound having the structure of Formula 9, a palladium catalyst, and a basic additive are reacted in a solvent to obtain the anthracene compound; the reaction temperature is 100℃~120℃, and the reaction time is 22h~26h. In some embodiments of this invention, the molar ratio of the boronized product, the compound having the structure of Formula 6, the palladium catalyst, and the basic additive is (5~15):(5~15):0.4:150, wherein the boronized product and the compound having the structure of Formula 8 react in a 1:1 molar ratio. In some embodiments of this invention, the basic additive includes at least one of potassium carbonate, potassium acetate, and potassium phosphate; the palladium catalyst includes at least one of Pd-132 and Pd(dppf)Cl2.

[0080] The preparation routes for the above anthracene compounds are as follows:

[0081]

[0082] In the first embodiment of the present invention, the compound having the structure of Formula 7 in the above-mentioned method for preparing anthracene compounds is specifically... When q is not 0, it is prepared by the following method:

[0083] A1) React the compound with the structure shown in formula (I-1) and the compound with the structure shown in formula (I-2) to obtain the compound with the structure shown in formula (I-3);

[0084]

[0085] B1) React the compound of formula (I-3) obtained in step A1) with the compound of structure (I-4) to obtain the compound of structure (I-5);

[0086]

[0087] C1) Combine the compound with the structure shown in formula (I-5) obtained in step B1) with X2-(Ar3). q -B(OH)2 reacts to give a compound with the structure of formula 7.

[0088] In the first embodiment described above, when q is 0, step C1) is unnecessary, and the compound with the structure shown in formula (I-5) obtained in step B1) is the compound with the structure of formula 7. In the first embodiment described above, X2, Ar3, R1, and q are the same as described above and will not be repeated.

[0089] Step A1) above specifically involves reacting the compound with the structure shown in formula (I-1), the compound with the structure shown in formula (I-2), and sodium metabisulfite in a solvent to obtain the compound with the structure shown in formula (I-3); the reaction temperature is 90–110°C, and the reaction time is 9–11 h. In some embodiments of the present invention, the ratio of the compound with the structure shown in formula (I-1), the compound with the structure shown in formula (I-2), sodium metabisulfite, and the solvent is (40–80) mmol:(40–80) mmol:(80–160) mmol:(100–200) mL, wherein the molar ratio of the compound with the structure shown in formula (I-1) to the compound with the structure shown in formula (I-2) is 1:1. In some embodiments of the present invention, the solvent includes N,N-dimethylformamide.

[0090] After obtaining the compound with the structure shown in formula (I-3), step B1) is performed. Step B1) specifically involves reacting the obtained compound with the structure shown in formula (I-3), the compound with the structure shown in formula (I-4), a palladium catalyst, and a basic additive in a solvent to obtain the compound with the structure shown in formula (I-5). The reaction temperature is 100°C to 120°C, and the reaction time is 22h to 26h. In some embodiments of the present invention, the ratio of the obtained compound with the structure shown in formula (I-3), the compound with the structure shown in formula (I-4), the palladium catalyst, the basic additive, and the solvent is (5-30) mmol: (5-30) mmol: 0.4 mmol: 150 mmol: 90 mL, wherein the obtained compound with the structure shown in formula (I-3) and the compound with the structure shown in formula (I-4) react in a 1:1 molar ratio. In some embodiments of the present invention, the alkaline additive includes at least one of potassium carbonate, potassium acetate, and potassium phosphate; the palladium catalyst includes at least one of Pd-132, Pd(dppf)Cl2, and Pd(dtbpf)Cl2.

[0091] After obtaining the compound with the structure shown in formula (I-5), step C1) is performed. Specifically, step C1) involves: mixing the obtained compound with the structure shown in formula (I-5) with X2-(Ar3). q -B(OH)₂, an alkaline additive, and a solvent are reacted to obtain a compound having the structure of formula 7; the reaction temperature is 100℃~120℃, and the reaction time is 22h~26h. In some embodiments of the present invention, the obtained compound with the structure shown in formula (I-5), X₂-(Ar₃) qThe ratio of -B(OH)2, alkaline additive, and solvent is (5-30) mmol: (5-30) mmol: 0.4 mmol: 150 mmol: 90 mL. In some embodiments of the present invention, the alkaline additive includes at least one of potassium carbonate, potassium acetate, and potassium phosphate; the palladium catalyst includes at least one of Pd-132, Pd(dppf)Cl2, and Pd(dtbpf)Cl2.

[0092] The route for preparing the compound having the structure of Formula 7 according to the first embodiment described above is as follows:

[0093]

[0094] In the first embodiment described above, when R1 is a benzene-substituted benzimazole, it can be achieved by combining a compound with the structure shown in formula (Z-1a) and The compound with the structure shown in formula (I-5) was obtained by reacting according to a 1:2 molar ratio, and then subsequent steps were performed to obtain the compound with the structure of formula 7.

[0095]

[0096] In the second embodiment of the present invention, the compound having the structure of Formula 7 in the above-mentioned method for preparing anthracene compounds is specifically... When q is not 0, it is prepared by the following method:

[0097] A2) React the compound with the structure shown in formula (II-1) and the compound with the structure shown in formula (II-2) to obtain the compound with the structure shown in formula (II-3);

[0098]

[0099] B2) React the compound of formula (II-3) obtained in step A2) with the compound of structure (II-4) to obtain the compound of structure (II-5);

[0100]

[0101] C2) Combine the compound with the structure shown in formula (II-5) obtained in step B2) with X2-(Ar3). q -B(OH)2 reacts to give a compound with the structure of formula 7.

[0102] In the above-described method for preparing compounds with the structure of Formula 7, when q is 0, step C2) is unnecessary, and the compound with the structure shown in Formula (II-5) obtained in step B2) is the compound with the structure of Formula 7. In the second embodiment described above, X2, Ar3, R1, and q are the same as described above and will not be repeated.

[0103] Compared with step A1 of the first embodiment, step A2 of the second embodiment is the same except that the compound with the structure shown in formula (I-1) and the product obtained from the reaction (with the structure shown in formula (I-3)) are replaced with the compound with the structure shown in formula (II-1) and the compound with the structure shown in formula (II-3), respectively. The rest will not be described again.

[0104] Compared with step B1 of the first embodiment, step B2 of the second embodiment is the same except that the compound shown in formula (I-3) and the product obtained by the reaction (the compound with the structure shown in formula (I-5)) are replaced with the compound shown in formula (II-3) and the compound shown in formula (II-5) respectively, and the compound shown in formula (II-3) and the compound with the structure shown in formula (II-4) are reacted in a molar ratio of 1:2. All other aspects are the same and will not be described again.

[0105] Compared with step C1 of the first embodiment, step C2 of the second embodiment is the same except that the compound with the structure shown in formula (I-5) is replaced with the compound with the structure shown in formula (II-5) and the product obtained from the reaction is different. Therefore, it will not be described again.

[0106] The route for preparing the compound having the structure of Formula 7 according to the second embodiment described above is as follows:

[0107]

[0108] In the second embodiment described above, when R1 is a benzene-substituted benzimazole, it can be achieved by combining a compound with the structure shown in formula (Z-2a) and The compound with the structure shown in formula (Z-3a) was obtained by reacting according to a 1:2 molar ratio. Then, the compound with the structure shown in formula (Z-3a) was formylated to obtain the compound shown in formula (Z-4a). The compound shown in formula (Z-4a) and... The compound with the structure shown in formula (II-5) was obtained by reacting according to a 1:1 molar ratio, and the compound with the structure of formula 7 was obtained by subsequent steps.

[0109]

[0110] In the third embodiment of the present invention, the compound having the structure of Formula 9 in the above-mentioned method for preparing anthracene compounds is specifically... When z is 1, and p is not 0, it is prepared by the following method:

[0111] A3) React the compound with the structure shown in formula (A-1) and the compound with the structure shown in formula (A-2) to obtain the compound with the structure shown in formula (A-3);

[0112]

[0113] B3) React the compound of formula (A-3) obtained in step A3) with the compound of structure (A-4) to obtain the compound of structure (A-5);

[0114]

[0115] C3) Combine the compound of formula (A-5) obtained in step B3) with X3-(Ar4). p -B(OH)2 reacts to give a compound with the structure of formula 9.

[0116] In the third embodiment described above, when p is 0, step C3) is unnecessary, and the compound with the structure shown in formula (A-5) obtained in step B3) is the compound with the structure of formula 9. In the third embodiment described above, X3, Ar4, R3, and p are the same as described above and will not be repeated.

[0117] Step A3) above specifically involves reacting the compound with the structure shown in formula (A-1), the compound with the structure shown in formula (A-2), and sodium metabisulfite in a solvent to obtain the compound with the structure shown in formula (A-3); the reaction temperature is 90–110°C, and the reaction time is 9–11 h. In some embodiments of the present invention, the ratio of the compound with the structure shown in formula (A-1), the compound with the structure shown in formula (A-2), sodium metabisulfite, and the solvent is (40–80) mmol:(40–80) mmol:(80–160) mmol:(100–200) mL, wherein the molar ratio of the compound with the structure shown in formula (A-1) to the compound with the structure shown in formula (A-2) is 1:1. In some embodiments of the present invention, the solvent includes N,N-dimethylformamide.

[0118] After obtaining the compound with the structure shown in formula (A-3), step B3) is performed. Specifically, step B3) involves reacting the obtained compound with the structure shown in formula (A-3), the compound with the structure shown in formula (A-4), a palladium catalyst, and a basic additive in a solvent to obtain the compound with the structure shown in formula (A-5). The reaction temperature is 100°C to 120°C, and the reaction time is 22 h to 26 h. In some embodiments of the present invention, the ratio of the obtained compound with the structure shown in formula (A-3), the compound with the structure shown in formula (A-4), the palladium catalyst, the basic additive, and the solvent is (5–30) mmol: (5–30) mmol: 0.4 mmol: 150 mmol: 90 mL, wherein the obtained compound with the structure shown in formula (A-3) and the compound with the structure shown in formula (A-4) react in a 1:1 molar ratio. In some embodiments of the present invention, the alkaline additive includes at least one of potassium carbonate, potassium acetate, and potassium phosphate; the palladium catalyst includes at least one of Pd-132, Pd(dppf)Cl2, and Pd(dtbpf)Cl2.

[0119] After obtaining the compound with the structure shown in formula (A-5), step C3) is performed. Specifically, step C3) involves: mixing the obtained compound with the structure shown in formula (A-5) with X3-(Ar4). p -B(OH)₂, an alkaline additive, and a solvent are reacted to obtain a compound having the structure of formula 9; the reaction temperature is 100℃~120℃, and the reaction time is 22h~26h. In some embodiments of the present invention, the obtained compound with the structure shown in formula (A-5), X3-(Ar4) p The ratio of -B(OH)2, alkaline additive, and solvent is (5-30) mmol: (5-30) mmol: 0.4 mmol: 150 mmol: 90 mL. In some embodiments of the present invention, the alkaline additive includes at least one of potassium carbonate, potassium acetate, and potassium phosphate; the palladium catalyst includes at least one of Pd-132, Pd(dppf)Cl2, and Pd(dtbpf)Cl2.

[0120] The route for preparing the compound having the structure of Formula 9 in the third embodiment described above is as follows:

[0121]

[0122] In the third embodiment described above, when R3 is a benzene-substituted benzimazole, it can be achieved by combining a compound with the structure shown in formula (Z-1b) and The compound with the structure shown in formula (A-5) was obtained by reacting according to a 1:2 molar ratio, and then subsequent steps were performed to obtain the compound having the structure of formula 9;

[0123]

[0124] In the fourth embodiment of the present invention, the compound having the structure of Formula 9 in the above-described method for preparing anthracene compounds is specifically... When z is 1, and p is not 0, it is prepared by the following method:

[0125] A4) React the compound with the structure shown in formula (B-1) and the compound with the structure shown in formula (B-2) to obtain the compound with the structure shown in formula (B-3);

[0126]

[0127] B4) React the compound of formula (B-3) obtained in step A4) with the compound of structure (B-4) to obtain the compound of structure (B-5).

[0128]

[0129] C4) Combine the compound of formula (B-5) obtained in step B4) with X3-(Ar4). p -B(OH)2 reacts to give a compound with the structure of formula 9.

[0130] In the fourth embodiment described above, when p is 0, step C4) is unnecessary, and the compound with the structure shown in formula (B-5) obtained in step B4) is the compound with the structure of formula 9. In the fourth embodiment described above, X3, Ar4, R3, and p are the same as described above and will not be repeated.

[0131] Compared with step A3 of the third embodiment, step A4 of the fourth embodiment is the same except that the compound with the structure shown in formula (A-1) and the product obtained from the reaction (with the structure shown in formula (A-3)) are replaced with the compound with the structure shown in formula (B-1) and the compound with the structure shown in formula (B-3), respectively. The rest will not be described again.

[0132] Compared with step B3 of the first embodiment, step B4 of the fourth embodiment is the same except that the compound shown in formula (A-3) and the product obtained by the reaction (the compound with the structure shown in formula (A-5)) are replaced with the compound shown in formula (B-3) and the compound shown in formula (B-5) respectively, and the compound shown in formula (B-3) and the compound with the structure shown in formula (B-4) are reacted in a molar ratio of 1:2. All other aspects are the same and will not be described again.

[0133] Compared with step C3 of the first embodiment, step C4) of the fourth embodiment is the same except that the compound with the structure shown in formula (A-5) is replaced with the compound with the structure shown in formula (B-5) and the product obtained from the reaction is different. Therefore, it will not be described again.

[0134] The route for preparing the compound having the structure of Formula 9 according to the fourth embodiment described above is as follows:

[0135]

[0136] In the fourth embodiment described above, when R3 is a benzene-substituted benzimazole, it can be achieved by combining a compound with the structure shown in formula (Z-2b) and The compound with the structure shown in formula (Z-3b) was obtained by reacting according to a 1:2 molar ratio. Then, the compound with the structure shown in formula (Z-3a) was formylated to obtain the compound shown in formula (Z-4b). The compound shown in formula (Z-4b) and... The compound with the structure shown in formula (B-5) was obtained by reacting according to a 1:1 molar ratio, and the compound with the structure of formula 9 was obtained by subsequent steps.

[0137]

[0138]

[0139] This invention provides the application of anthracene compounds as electron transport host materials in electroluminescent devices, as described in any of the above technical solutions.

[0140] The present invention also provides an electroluminescent device, comprising an anode, a cathode, and an organic thin film layer located between the anode and the cathode; the organic thin film layer comprises anthracene compounds as described in any of the above-described technical solutions. Specifically, the organic thin film layer comprises a light-emitting layer; the light-emitting layer comprises anthracene compounds as described in any of the above-described technical solutions and a blue light-emitting dye; the blue light-emitting dye comprises conventional fluorescent dyes and multiple resonance thermally activated delayed fluorescent dyes.

[0141] The present invention also provides the application of anthracene compounds as electron transport host materials in flat panel display devices, flexible display devices, or lighting sources, as described in any of the above technical solutions.

[0142] This invention provides an anthracene compound, its preparation method, and its applications. The anthracene compound provided by this invention contains the electron transport unit benzimidazole, which can promote electron injection and transport in the light-emitting layer of the device, promote charge transport balance between holes and electrons, and reduce the driving voltage. By introducing a sterically hindered group at the ortho position of the benzimidazole electron transport unit, the torsion angle between the anthracene unit and benzimidazole is increased, thereby reducing their conjugation degree and avoiding the electron-withdrawing effect of benzimidazole from altering the excited-state characteristics of the anthracene unit, ensuring its efficient triplet exciton upconversion properties, and guaranteeing high exciton utilization and blue light emission of the anthracene group. Simultaneously, benzimidazole, as an excellent electron transport unit, can effectively enhance the host electron transport capability and promote charge transport balance in the electroluminescent device. Based on the above-mentioned working principle, the anthracene compound provided by this invention is used as an electron transport host material for blue dyes, and the resulting electroluminescent device exhibits high luminous efficiency and low driving voltage. Experiments show that the anthracene compounds provided by this invention, when used as electron transport host materials for blue light dyes, result in electroluminescent devices with a turn-on voltage as low as 2.7V and a maximum external quantum efficiency of over 12%. Detailed Implementation

[0143] This invention discloses an anthracene compound, its preparation method, and its applications. Those skilled in the art can refer to this document and appropriately modify the process parameters to achieve the desired results. It should be particularly noted that all similar substitutions and modifications are obvious to those skilled in the art and are considered to be included in this invention. The methods and applications of this invention have been described through preferred embodiments, and those skilled in the art can clearly modify or appropriately change and combine the methods and applications described herein without departing from the content, spirit, and scope of this invention to realize and apply the technology of this invention.

[0144] The present invention will be further described below with reference to the embodiments:

[0145] Example 1

[0146] The reaction is as follows:

[0147]

[0148] Under an argon atmosphere, 1-1 (12.4 g, 40 mmol), 1-2 (7.4 g, 40 mmol), 15.2 g sodium metabisulfite (80 mmol), and N,N-dimethylformamide (100 mL) were added to a 250 mL round-bottom flask. The mixture was heated and stirred at 100 °C for 10 hours. After the reaction solution cooled to room temperature, it was poured into cold water and extracted three times with ethyl acetate (3 × 50 mL). The organic phase was separated, and the product compound 1-3 (15.0 g, 79% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical value C, 48.03; H, 2.55; N, 5.90; Measured value C, 48.00; H, 2.52; N, 5.85. Mass spectrometry: Theoretical value 473.92; Measured value 473.9 (M+).

[0149] Under an argon atmosphere, compounds 1-3 (14.3 g, 30 mmol), 1-4 (1.8 g, 30 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 1-5 (8.9 g, 82% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 66.16; H, 4.16; N, 7.71; Measured C, 66.19; H, 4.11; N, 7.70. Mass spectrometry: Theoretical 362.04; Measured 362.0 (M+).

[0150] Under an argon atmosphere, compounds 1-5 (8.7 g, 24 mmol), 1-6 (4.8 g, 24 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 1-7 (8.1 g, 77% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical value C, 71.08; H, 4.36; N, 6.38; Measured value C, 71.00; H, 4.46; N, 6.32. Mass spectrometry: Theoretical value 438.07; Measured value 438.0 (M+).

[0151] Under an argon atmosphere, compounds 1-7 (7.9 g, 18 mmol), 1-8 (5.4 g, 18 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 1-9 (8.8 g, 79% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical value C, 78.05; H, 4.42; N, 4.55; Measured value C, 78.00; H, 4.42; N, 4.65. Mass spectrometry: Theoretical value 614.14; Measured value 614.1 (M+).

[0152] Under an argon atmosphere, compounds 1-9 (8.6 g, 14 mmol), pinacol diborate (8.9 g, 35 mmol), potassium acetate (3.4 g, 35 mmol), dioxane (120 mL), and Pd(dppf)Cl2 (0.5 g, 0.7 mmol) were added to a 250 mL round-bottom flask and heated to reflux for 12 hours. After the reaction was complete, the mixture was cooled, the solvent was removed, and the product was hydrolyzed with an aqueous sodium hydroxide solution. The product was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain compound 1-10 (7.0 g, 86% yield). Elemental analysis: Theoretical value C, 82.76; H, 5.04; N, 4.83; Measured value C, 82.70; H, 5.00; N, 4.81. Mass spectrometry: Theoretical value 580.23; Measured value 580.2 (M+).

[0153] Under an argon atmosphere, 1-10 (6.4 g, 11 mmol), 1-11 (1.8 g, 11 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound H-1 (5.1 g, 75% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical value C, 89.43; H, 6.04; N, 4.53; Measured value C, 89.47; H, 6.01; N, 4.50. Mass spectrometry: Theoretical value 617.29; Measured value 617.2 (M+).

[0154] Example 2

[0155] The reaction is as follows:

[0156]

[0157] Under an argon atmosphere, 2-1 (12.4 g, 40 mmol), 2-2 (7.4 g, 40 mmol), 15.2 g sodium metabisulfite (80 mmol), and N,N-dimethylformamide (100 mL) were added to a 250 mL round-bottom flask. The mixture was heated and stirred at 100 °C for 10 hours. After the reaction solution cooled to room temperature, it was poured into cold water and extracted three times with ethyl acetate (3 × 50 mL). The organic phase was separated, and the product compound 2-3 (16.1 g, 83% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical value C, 48.03; H, 2.55; N, 5.90; Measured value C, 48.00; H, 2.50; N, 5.81. Mass spectrometry: Theoretical value 473.92; Measured value 473.9 (M+).

[0158] Under an argon atmosphere, compounds 2-3 (15.2 g, 32 mmol), 2-4 (3.9 g, 32 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 2-5 (10.5 g, 77% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 70.60; H, 4.03; N, 6.59; Observed values: 70.61; H, 4.09; N, 6.54. Mass spectrometry: Theoretical 426.06; Observed 426.0 (M+).

[0159] Under an argon atmosphere, compounds 2-5 (9.8 g, 23 mmol), 2-6 (6.9 g, 23 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 2-7 (10.5 g, 76% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 77.87; H, 4.19; N, 4.66; Measured C, 77.87; H, 4.19; N, 4.66. Mass spectrometry: Theoretical 600.12; Measured 600.0 (M+).

[0160] Under an argon atmosphere, 2-7 (9.6 g, 16 mmol), pinacol diborate (8.9 g, 35 mmol), potassium acetate (3.4 g, 35 mmol), dioxane (120 mL), and Pd(dppf)Cl2 (0.5 g, 0.7 mmol) were added to a 250 mL round-bottom flask and heated to reflux for 12 hours. After the reaction was complete, the mixture was cooled, the solvent was removed, and the product was hydrolyzed with an aqueous sodium hydroxide solution. The product was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain compound 2-8 (7.0 g, 77% yield). Elemental analysis: Theoretical value C, 82.69; H, 4.80; N, 4.95; Measured value C, 82.65; H, 4.89; N, 4.94. Mass spectrometry: Theoretical value 566.22; Measured value 566.2 (M+).

[0161] Under an argon atmosphere, 2-8 (6.2 g, 11 mmol), 2-9 (1.8 g, 11 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound H-3 (4.9 g, 74% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 89.52; H, 5.84; N, 4.64; Measured C, 89.50; H, 5.81; N, 4.68. Mass spectrometry: Theoretical 603.27; Measured 603.2 (M+).

[0162] Example 3

[0163] The reaction is as follows:

[0164]

[0165] Under an argon atmosphere, 3-1 (12.4 g, 40 mmol), 3-2 (7.4 g, 40 mmol), 15.2 g sodium metabisulfite (80 mmol), and N,N-dimethylformamide (100 mL) were added to a 250 mL round-bottom flask. The mixture was heated and stirred at 100 °C for 10 hours. After the reaction solution cooled to room temperature, it was poured into cold water and extracted three times with ethyl acetate (3 × 50 mL). The organic phase was separated, and the product compound 3-3 (15.4 g, 81% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical value C, 48.03; H, 2.55; N, 5.90; Measured value C, 48.01; H, 2.52; N, 5.89. Mass spectrometry: Theoretical value 473.92; Measured value 473.9 (M+).

[0166] Under an argon atmosphere, 3-3 (15.2 g, 32 mmol), 3-4 (3.9 g, 32 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 3-5 (10.6 g, 78% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 70.60; H, 4.06; N, 6.59; Measured C, 70.65; H, 4.07; N, 6.58. Mass spectrometry: Theoretical 424.06; Measured 424.0 (M+).

[0167] Under an argon atmosphere, compounds 3-5 (5.5 g, 13 mmol), 3-6 (3.9 g, 13 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 3-7 (5.8 g, 74% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical value C, 77.87; H, 4.19; N, 4.66; Measured value C, 77.84; H, 4.10; N, 4.68. Mass spectrometry: Theoretical value; Measured value (M+).

[0168] Under an argon atmosphere, 3-7 (5.4 g, 9 mmol), pinacol diborate (8.9 g, 35 mmol), potassium acetate (3.4 g, 35 mmol), dioxane (120 mL), and Pd(dppf)Cl2 (0.5 g, 0.7 mmol) were added to a 250 mL round-bottom flask and heated to reflux for 12 hours. After the reaction was complete, the mixture was cooled, the solvent was removed, and the product was hydrolyzed with an aqueous sodium hydroxide solution. The product was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain compound 3-8 (4.4 g, 86% yield). Elemental analysis: Theoretical C, 82.69; H, 4.80; N, 4.95; Measured C, 82.65; H, 4.84; N, 4.90. Mass spectrometry: Theoretical 566.22; Measured 566.2 (M+).

[0169] Under an argon atmosphere, 3-8 (4.0 g, 7 mmol), 3-5 (3.0 g, 7 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound H-6 (4.6 g, 76% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 88.66; H, 4.88; N, 6.46; Measured C, 88.62; H, 4.84; N, 6.43. Mass spectrometry: Theoretical 866.34; Measured 866.3 (M+).

[0170] Example 4

[0171] The reaction is as follows:

[0172]

[0173] Under an argon atmosphere, 4-1 (12.4 g, 40 mmol), 4-2 (7.4 g, 40 mmol), 15.2 g sodium metabisulfite (80 mmol), and N,N-dimethylformamide (100 mL) were added to a 250 mL round-bottom flask. The mixture was heated and stirred at 100 °C for 10 hours. After the reaction solution cooled to room temperature, it was poured into cold water and extracted three times with ethyl acetate (3 × 50 mL). The organic phase was separated, and the product compound 4-3 (15.5 g, 82% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical value C, 48.03; H, 2.55; N, 5.90; Measured value C, 48.01; H, 2.50; N, 5.84. Mass spectrometry: Theoretical value 473.92; Measured value 473.9 (M+).

[0174] Under an argon atmosphere, 4-3 (15.2 g, 32 mmol), 4-4 (1.9 g, 32 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 4-5 (9.2 g, 79% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 66.13; H, 4.16; N, 7.71; Measured C, 66.08; H, 4.15; N, 7.79. Mass spectrometry: Theoretical 362.04; Measured 362.0 (M+).

[0175] Under an argon atmosphere, compounds 4-5 (8.7 g, 24 mmol), 4-6 (7.2 g, 24 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 4-7 (9.8 g, 76% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 75.70; H, 4.30; N, 5.19; Measured C, 75.75; H, 4.20; N, 5.15. Mass spectrometry: Theoretical 538.10; Measured 538.1 (M+).

[0176] Under an argon atmosphere, 4-7 (8.6 g, 16 mmol), pinacol diborate (8.9 g, 35 mmol), potassium acetate (3.4 g, 35 mmol), dioxane (120 mL), and Pd(dppf)Cl2 (0.5 g, 0.7 mmol) were added to a 250 mL round-bottom flask and heated to reflux for 12 hours. After the reaction was complete, the mixture was cooled, the solvent was removed, and the product was hydrolyzed with an aqueous sodium hydroxide solution. The product was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain compound 4-8 (6.4 g, 79% yield). Elemental analysis: Theoretical C, 80.96; H, 5.00; N, 5.55; Measured C, 80.98; H, 5.05; N, 5.51. Mass spectrometry: Theoretical 504.20; Measured 504.2 (M+).

[0177] Under an argon atmosphere, 4-8 (5.0 g, 10 mmol), 4-9 (2.1 g, 10 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound H-7 (4.6 g, 78% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical value C, 90.07; H, 5.15; N, 4.77; Measured value C, 90.08; H, 5.14; N, 4.70. Mass spectrometry: Theoretical value 586.24; Measured value 586.2 (M+).

[0178] Example 5

[0179] The reaction is as follows:

[0180]

[0181] Under an argon atmosphere, 5-1 (13.6 g, 40 mmol), 5-2 (14.7 g, 80 mmol), 19.0 g sodium metabisulfite (100 mmol), and N,N-dimethylformamide (140 mL) were added to a 250 mL round-bottom flask. The mixture was heated and stirred at 100 °C for 10 hours. After the reaction solution cooled to room temperature, it was poured into cold water and extracted three times with ethyl acetate (3 × 50 mL). The organic phase was separated, and the product compound 5-3 (21.8 g, 82% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical value C, 57.59; H, 3.02; N, 8.40; Measured value C, 57.55; H, 3.07; N, 8.42. Mass spectrometry: Theoretical value 665.99; Measured value 665.9 (M+).

[0182] Under an argon atmosphere, 5-3 (21.3 g, 32 mmol), 5-4 (6.8 g, 32 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 5-5 (16.7 g, 74% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical value C, 74.68; H, 3.85; N, 7.92; Measured value C, 74.65; H, 3.81; N, 7.90. Mass spectrometry: Theoretical value 706.14; Measured value (M+).

[0183] Under an argon atmosphere, 5-5 (15.5 g, 22 mmol), 5-6 (6.6 g, 22 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 5-7 (14.6 g, 75% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 78.82; H, 3.99; N, 6.34; Measured C, 78.80; H, 3.97; N, 6.38. Mass spectrometry: Theoretical 882.20; Measured 882.2 (M+).

[0184] Under an argon atmosphere, compounds 5-7 (13.2 g, 15 mmol), pinacol diborate (8.9 g, 35 mmol), potassium acetate (3.4 g, 35 mmol), dioxane (120 mL), and Pd(dppf)Cl2 (0.5 g, 0.7 mmol) were added to a 250 mL round-bottom flask and heated to reflux for 12 hours. After the reaction was complete, the mixture was cooled, the solvent was removed, and the product was hydrolyzed with an aqueous sodium hydroxide solution. The product was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain compound 5-8 (10.4 g, 82% yield). Elemental analysis: Theoretical C, 82.08; H, 4.39; N, 6.60; Measured C, 82.05; H, 4.31; N, 6.57. Mass spectrometry: Theoretical 848.30; Measured 848.3 (M+).

[0185] Under an argon atmosphere, 5-8 (10.2 g, 12 mmol), 5-9 (2.5 g, 12 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound H-8 (8.5 g, yield 76%) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 87.72; H, 4.55; N, 6.02; Measured C, 87.70; H, 4.57; N, 6.56. Mass spectrometry: Theoretical 930.34; Measured 930.3 (M+).

[0186] Example 6

[0187] The reaction is as follows:

[0188]

[0189] Under an argon atmosphere, 6-1 (12.4 g, 40 mmol), 6-2 (7.4 g, 40 mmol), 15.2 g sodium metabisulfite (80 mmol), and N,N-dimethylformamide (100 mL) were added to a 250 mL round-bottom flask. The mixture was heated and stirred at 100 °C for 10 hours. After the reaction solution cooled to room temperature, it was poured into cold water and extracted three times with ethyl acetate (3 × 50 mL). The organic phase was separated, and the product compound 6-3 (15.2 g, 80% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical value C, 48.03; H, 2.55; N, 5.90; Measured value C, 48.00; H, 2.55; N, 5.82. Mass spectrometry: Theoretical value 473.92; Measured value 473.9 (M+).

[0190] Under an argon atmosphere, 6-3 (14.2 g, 30 mmol), 6-4 (8.3 g, 30 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 6-5 (13.0 g, 75% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 70.35; H, 3.82; N, 12.06; Measured C, 70.31; H, 3.80; N, 12.05. Mass spectrometry: Theoretical 579.11; Measured 579.1 (M+).

[0191] Under an argon atmosphere, 6-5 (11.6 g, 20 mmol), 6-6 (6.0 g, 20 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 6-7 (11.2 g, 74% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 76.19; H, 4.00; N, 9.26; Measured C, 76.12; H, 4.05; N, 9.27. Mass spectrometry: Theoretical 755.17; Measured 755.1 (M+).

[0192] Under an argon atmosphere, compounds 6-7 (9.8 g, 13 mmol), pinacol diborate (8.9 g, 35 mmol), potassium acetate (3.4 g, 35 mmol), dioxane (120 mL), and Pd(dppf)Cl2 (0.5 g, 0.7 mmol) were added to a 250 mL round-bottom flask and heated to reflux for 12 hours. After the reaction was complete, the mixture was cooled, the solvent was removed, and the product was hydrolyzed with an aqueous sodium hydroxide solution. The solution was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to give compound 6-8 (7.4 g, 79% yield). Elemental analysis: Theoretical C, 79.89; H, 4.47; N, 9.71; Measured C, 79.85; H, 4.42; N, 9.76. Mass spectrometry: Theoretical 721.26; Measured 721.2 (M+).

[0193] Under an argon atmosphere, 6-8 (5.8 g, 8 mmol), 6-9 (1.6 g, 8 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound H-9 (5.0 g, 78% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 86.65; H, 4.64; N, 8.71; Measured C, 86.68; H, 4.67; N, 8.70. Mass spectrometry: Theoretical 803.30; Measured 803.3 (M+).

[0194] Example 7

[0195] The reaction is as follows:

[0196]

[0197] Under an argon atmosphere, 7-1 (12.4 g, 40 mmol), 7-2 (7.4 g, 40 mmol), 15.2 g sodium metabisulfite (80 mmol), and N,N-dimethylformamide (100 mL) were added to a 250 mL round-bottom flask. The mixture was heated and stirred at 100 °C for 10 hours. After the reaction solution cooled to room temperature, it was poured into cold water and extracted three times with ethyl acetate (3 × 50 mL). The organic phase was separated, and the product compound 7-3 (15.8 g, 83% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical value C, 48.03; H, 2.55; N, 5.90; Measured value C, 48.05; H, 2.54; N, 5.89. Mass spectrometry: Theoretical value 473.92; Measured value 473.9 (M+).

[0198] Under an argon atmosphere, 7-3 (15.2 g, 32 mmol), 7-4 (7.3 g, 32 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 7-5 (13.8 g, 81% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 70.06; H, 3.60; N, 5.27; Measured C, 70.01; H, 3.62; N, 5.24. Mass spectrometry: Theoretical 532.04; Measured 532.0 (M+).

[0199] Under an argon atmosphere, 7-5 (7.4 g, 14 mmol), 7-6 (4.2 g, 14 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 7-7 (7.9 g, 80% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 76.37; H, 3.85; N, 3.96; Measured C, 76.35; H, 3.81; N, 3.98. Mass spectrometry: Theoretical 708.11; Measured 708.1 (M+).

[0200] Under an argon atmosphere, 7-7 (7.4 g, 10.5 mmol), pinacol diborate (8.9 g, 35 mmol), potassium acetate (3.4 g, 35 mmol), dioxane (120 mL), and Pd(dppf)Cl2 (0.5 g, 0.7 mmol) were added to a 250 mL round-bottom flask and heated to reflux for 12 hours. After the reaction was complete, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The product was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain compound 7-8 (5.8 g, 82% yield). Elemental analysis: Theoretical value C, 80.36; H, 4.35; N, 4.16; Measured value C, 80.31; H, 4.30; N, 4.12. Mass spectrometry: Theoretical value 672.20; Measured value 672.2 (M+).

[0201] Under an argon atmosphere, 7-8 (5.4 g, 8 mmol), 7-5 (4.3 g, 8 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound H-12 (6.2 g, 72% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 84.57; H, 4.30; N, 5.19; Measured C, 84.54; H, 4.31; N, 5.17. Mass spectrometry: Theoretical 1078.32; Measured 1078.3 (M+).

[0202] Example 8

[0203] The reaction is as follows:

[0204]

[0205] Under an argon atmosphere, 8-1 (12.4 g, 40 mmol), 8-2 (7.4 g, 40 mmol), 15.2 g sodium metabisulfite (80 mmol), and N,N-dimethylformamide (100 mL) were added to a 250 mL round-bottom flask. The mixture was heated and stirred at 100 °C for 10 hours. After the reaction solution cooled to room temperature, it was poured into cold water and extracted three times with ethyl acetate (3 × 50 mL). The organic phase was separated, and the product compound 8-3 (16.0 g, 84% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical value C, 48.03; H, 2.55; N, 5.90; Measured value C, 48.04; H, 2.51; N, 5.82. Mass spectrometry: Theoretical value 473.92; Measured value 473.9 (M+).

[0206] Under an argon atmosphere, 8-3 (15.2 g, 32 mmol), 8-4 (6.8 g, 32 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 8-5 (12.9 g, 78% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical value C, 72.24; H, 3.72; N, 5.44; Measured value C, 72.24; H, 3.77; N, 5.49. Mass spectrometry: Theoretical value 516.07; Measured value 516.0 (M+).

[0207] Under an argon atmosphere, 8-6 (13.6 g, 40 mmol), 8-2 (14.7 g, 80 mmol), 19.0 g sodium metabisulfite (100 mmol), and N,N-dimethylformamide (140 mL) were added to a 250 mL round-bottom flask, and the mixture was heated and stirred at 100 °C for 10 hours. After the reaction solution cooled to room temperature, it was poured into cold water and extracted three times with ethyl acetate (3 × 50 mL). The organic phase was separated, and the product compound 8-7 (21.9 g, 82% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical value C, 57.59; H, 3.02; N, 8.40; Measured value C, 57.51; H, 3.05; N, 8.24. Mass spectrometry: Theoretical value 665.99; Measured value 665.9 (M+).

[0208] Under an argon atmosphere, 8-7 (21.4 g, 32 mmol), 8-4 (6.8 g, 32 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 8-8 (17.9 g, 79% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 74.68; H, 3.85; N, 7.92; Measured C, 74.65; H, 3.87; N, 7.90. Mass spectrometry: Theoretical 706.14; Measured 706.1 (M+).

[0209] Under an argon atmosphere, 8-8 (17.0 g, 24 mmol), 8-9 (7.2 g, 24 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 8-10 (16.1 g, 76% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 78.82; H, 3.99; N, 6.34; Measured C, 78.87; H, 3.90; N, 6.31. Mass spectrometry: Theoretical 882.20; Measured 882.2 (M+).

[0210] Under an argon atmosphere, 8-10 (15.0 g, 17 mmol), pinacol diborate (8.9 g, 35 mmol), potassium acetate (3.4 g, 35 mmol), dioxane (120 mL), and Pd(dppf)Cl2 (0.5 g, 0.7 mmol) were added to a 250 mL round-bottom flask and heated to reflux for 12 hours. After the reaction was complete, the mixture was cooled, the solvent was removed, and the product was hydrolyzed with an aqueous sodium hydroxide solution. The product was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain compound 8-11 (11.8 g, 82% yield). Elemental analysis: Theoretical C, 82.08; H, 4.39; N, 6.60; Measured C, 82.05; H, 4.34; N, 6.66. Mass spectrometry: Theoretical 848.30; Measured 848.3 (M+).

[0211] Under an argon atmosphere, 8-11 (10.2 g, 12 mmol), 8-5 (6.2 g, 12 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound H-20 (10.9 g, 73% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 86.25; H, 4.39; N, 6.78; Measured C, 86.22; H, 4.38; N, 6.74. Mass spectrometry: Theoretical 1238.43; Measured 1238.4 (M+).

[0212] Example 9

[0213] The reaction is as follows:

[0214]

[0215] Under an argon atmosphere, 9-1 (13.6 g, 40 mmol), 9-2 (14.7 g, 80 mmol), 19.0 g sodium metabisulfite (100 mmol), and N,N-dimethylformamide (140 mL) were added to a 250 mL round-bottom flask. The mixture was heated and stirred at 100 °C for 10 hours. After the reaction solution cooled to room temperature, it was poured into cold water and extracted three times with ethyl acetate (3 × 50 mL). The organic phase was separated, and the product compound 9-3 (21.6 g, 81% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical value C, 57.59; H, 3.02; N, 8.40; Measured value C, 57.54; H, 3.00; N, 8.29. Mass spectrometry: Theoretical value 665.99; Measured value 665.9 (M+).

[0216] Under an argon atmosphere, 9-3 (21.4 g, 32 mmol), 9-4 (3.9 g, 32 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 9-5 (15.6 g, 79% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 71.85; H, 3.91; N, 11.32; Measured C, 71.89; H, 3.94; N, 11.37. Mass spectrometry: Theoretical 617.12; Measured 617.1 (M+).

[0217] Under an argon atmosphere, 9-5 (8.7 g, 14 mmol), 9-6 (4.2 g, 14 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 9-7 (8.5 g, 76% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 77.08; H, 4.06; N, 8.81; Measured C, 77.04; H, 4.07; N, 8.80. Mass spectrometry: Theoretical 793.18; Measured 793.1 (M+).

[0218] Under an argon atmosphere, 9-7 (7.9 g, 10 mmol), pinacol diborate (8.9 g, 35 mmol), potassium acetate (3.4 g, 35 mmol), dioxane (120 mL), and Pd(dppf)Cl2 (0.5 g, 0.7 mmol) were added to a 250 mL round-bottom flask and heated to reflux for 12 hours. After the reaction was complete, the mixture was cooled, the solvent was removed, and the product was hydrolyzed with an aqueous sodium hydroxide solution. The product was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain compound 9-8 (5.9 g, 78% yield). Elemental analysis: Theoretical C, 80.63; H, 4.51; N, 9.22; Measured C, 80.67; H, 4.56; N, 9.20. Mass spectrometry: Theoretical 759.28; Measured 759.2 (M+).

[0219] Under an argon atmosphere, 9-8 (5.3 g, 7 mmol), 9-5 (4.3 g, 7 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound H-24 (6.6 g, 75% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 84.32; H, 4.50; N, 11.17; Measured C, 84.35; H, 4.54; N, 11.12. Mass spectrometry: Theoretical 1252.47; Measured 1252.4 (M+).

[0220] Example 10

[0221] The reaction is as follows:

[0222]

[0223] Under an argon atmosphere, 10⁻¹ (12.4 g, 40 mmol), 10⁻² (7.4 g, 40 mmol), 15.2 g sodium metabisulfite (80 mmol), and N,N-dimethylformamide (100 mL) were added to a 250 mL round-bottom flask, and the mixture was heated and stirred at 100 °C for 10 hours. After the reaction solution cooled to room temperature, it was poured into cold water and extracted three times with ethyl acetate (3 × 50 mL). The organic phase was separated, and the product compound 10⁻³ (15.2 g, 80% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical value C, 48.03; H, 2.55; N, 5.90; Measured value C, 48.08; H, 2.50; N, 5.86. Mass spectrometry: Theoretical value 473.92; Measured value 473.9 (M⁺).

[0224] Under an argon atmosphere, 10⁻³ (14.3 g, 30 mmol), 10⁻⁴ (8.3 g, 30 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 10⁻⁵ (13.8 g, 79% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical value C, 70.35; H, 3.82; N, 12.06; Measured value C, 70.31; H, 3.80; N, 12.06. Mass spectrometry: Theoretical value 579.11; Measured value 579.1 (M⁺).

[0225] Under an argon atmosphere, 10⁻⁵ (8.1 g, 14 mmol), 10⁻⁶ (4.2 g, 14 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 10⁻⁷ (7.9 g, 75% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 76.19; H, 4.00; N, 9.26; Measured C, 76.15; H, 4.07; N, 9.23. Mass spectrometry: Theoretical 755.17; Measured 755.1 (M⁺).

[0226] Under an argon atmosphere, 10⁻⁷ (7.2 g, 9.5 mmol), pinacol diborate (8.9 g, 35 mmol), potassium acetate (3.4 g, 35 mmol), dioxane (120 mL), and Pd(dppf)Cl₂ (0.5 g, 0.7 mmol) were added to a 250 mL round-bottom flask and heated to reflux for 12 hours. After the reaction was complete, the mixture was cooled, the solvent was removed, and the product was hydrolyzed with an aqueous sodium hydroxide solution. The solution was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain compound 10⁻⁸ (5.7 g, 83% yield). Elemental analysis: Theoretical C, 79.89; H, 4.47; N, 9.71; Measured C, 79.92; H, 4.45; N, 9.70. Mass spectrometry: Theoretical 721.26; Measured 721.2 (M⁺).

[0227] Under an argon atmosphere, 10⁻⁸ (5.1 g, 7 mmol), 10⁻⁹ (1.1 g, 7 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound H-25 (4.1 g, 77% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical value C, 86.03; H, 4.68; N, 9.29; Measured value C, 86.00; H, 4.64; N, 9.24. Mass spectrometry: Theoretical value 753.29; Measured value 753.2 (M⁺).

[0228] Example 11

[0229] The reaction is as follows:

[0230]

[0231] Under an argon atmosphere, 11-1 (13.6 g, 40 mmol), 11-2 (14.7 g, 80 mmol), 19.0 g sodium metabisulfite (100 mmol), and N,N-dimethylformamide (140 mL) were added to a 250 mL round-bottom flask, and the mixture was heated and stirred at 100 °C for 10 hours. After the reaction solution cooled to room temperature, it was poured into cold water and extracted three times with ethyl acetate (3 × 50 mL). The organic phase was separated, and the product compound 11-3 (21.6 g, 81% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical value C, 57.59; H, 3.02; N, 8.40; Measured value C, 57.51; H, 3.00; N, 8.20. Mass spectrometry: Theoretical value 665.99; Measured value 665.9 (M+).

[0232] Under an argon atmosphere, 11-3 (21.4 g, 32 mmol), 11-4 (1.9 g, 32 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 11-5 (13.9 g, 78% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 71.36; H, 4.17; N, 10.9; Measured C, 71.34; H, 4.12; N, 10.8. Mass spectrometry: Theoretical 554.11; Measured 554.1 (M+).

[0233] Under an argon atmosphere, 11-5 (7.8 g, 14 mmol), 11-6 (4.2 g, 14 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 11-7 (8.0 g, 78% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 77.15; H, 4.27; N, 7.66; Measured C, 77.14; H, 4.28; N, 7.66. Mass spectrometry: Theoretical 730.17; Measured 730.1 (M+).

[0234] Under an argon atmosphere, 11-7 (7.7 g, 10.5 mmol), pinacol diborate (8.9 g, 35 mmol), potassium acetate (3.4 g, 35 mmol), dioxane (120 mL), and Pd(dppf)Cl2 (0.5 g, 0.7 mmol) were added to a 250 mL round-bottom flask and heated to reflux for 12 hours. After the reaction was complete, the mixture was cooled, the solvent was removed, and the product was hydrolyzed with an aqueous sodium hydroxide solution. The product was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain compound 11-8 (5.8 g, 79% yield). Elemental analysis: Theoretical value C, 81.04; H, 4.78; N, 8.04; Measured value C, 81.01; H, 4.79; N, 8.00. Mass spectrometry: Theoretical value 696.27; Measured value 696.2 (M+).

[0235] Under an argon atmosphere, 11-8 (5.2 g, 7.5 mmol), 11-5 (4.2 g, 7.5 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound H-26 (5.8 g, 69% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 85.23; H, 4.83; N, 9.94; Measured C, 85.23; H, 4.83; N, 9.94. Mass spectrometry: Theoretical 1126.45; Measured 1126.4 (M+).

[0236] Example 12

[0237] The reaction is as follows:

[0238]

[0239] Under an argon atmosphere, 12-1 (12.4 g, 40 mmol), 12-2 (7.4 g, 40 mmol), 15.2 g sodium metabisulfite (80 mmol), and N,N-dimethylformamide (100 mL) were added to a 250 mL round-bottom flask. The mixture was heated and stirred at 100 °C for 10 hours. After the reaction solution cooled to room temperature, it was poured into cold water and extracted three times with ethyl acetate (3 × 50 mL). The organic phase was separated, and the product compound 12-3 (15.8 g, 83% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical value C, 48.03; H, 2.55; N, 5.90; Measured value C, 48.10; H, 2.05; N, 5.86. Mass spectrometry: Theoretical value 473.92; Measured value 473.9 (M+).

[0240] Under an argon atmosphere, 12-3 (15.2 g, 32 mmol), 12-4 (6.8 g, 32 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 12-5 (13.0 g, 79% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 72.24; H, 3.72; N, 5.44; Measured C, 72.20; H, 3.79; N, 5.46. Mass spectrometry: Theoretical 516.07; Measured 516.0 (M+).

[0241] Under an argon atmosphere, 12-5 (7.2 g, 14 mmol), 12-6 (4.2 g, 14 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 12-7 (7.6 g, 78% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 78.15; H, 3.94; N, 4.05; Measured C, 78.15; H, 3.94; N, 4.05. Mass spectrometry: Theoretical 690.13; Measured 690.1 (M+).

[0242] Under an argon atmosphere, 12-7 (6.9 g, 10 mmol), pinacol diborate (8.9 g, 35 mmol), potassium acetate (3.4 g, 35 mmol), dioxane (120 mL), and Pd(dppf)Cl2 (0.5 g, 0.7 mmol) were added to a 250 mL round-bottom flask and heated to reflux for 12 hours. After the reaction was complete, the mixture was cooled, the solvent was removed, and the product was hydrolyzed with an aqueous sodium hydroxide solution. The solution was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain compound 12-8 (5.4 g, 83% yield). Elemental analysis: Theoretical value C, 82.32; H, 4.45; N, 4.27; Measured value C, 82.30; H, 4.49; N, 4.25. Mass spectrometry: Theoretical value 656.23; Measured value 656.2 (M+).

[0243] Under an argon atmosphere, 12-8 (4.6 g, 7 mmol), 12-5 (3.6 g, 7 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound H-27 (5.4 g, 74% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 87.17; H, 4.43; N, 5.35; Measured C, 87.14; H, 4.40; N, 5.38. Mass spectrometry: Theoretical 1046.36; Measured 1046.3 (M+).

[0244] Example 13

[0245] The reaction is as follows:

[0246]

[0247] Under an argon atmosphere, 13-1 (12.4 g, 40 mmol), 13-2 (7.4 g, 40 mmol), 15.2 g sodium metabisulfite (80 mmol), and N,N-dimethylformamide (100 mL) were added to a 250 mL round-bottom flask. The mixture was heated and stirred at 100 °C for 10 hours. After the reaction solution cooled to room temperature, it was poured into cold water and extracted three times with ethyl acetate (3 × 50 mL). The organic phase was separated, and the product compound 13-3 (15.6 g, 82% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical value C, 48.03; H, 2.55; N, 5.90; Measured value C, 48.05; H, 2.54; N, 5.81. Mass spectrometry: Theoretical value 473.92; Measured value 473.9 (M+).

[0248] Under an argon atmosphere, 13-3 (15.2 g, 32 mmol), 13-4 (1.9 g, 32 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 13-5 (9.4 g, 81% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 66.13; H, 4.16; N, 7.71 (test value). Mass spectrometry: Theoretical 362.04, experimental 362.0 (M+).

[0249] Under an argon atmosphere, 13-5 (9.1 g, 25 mmol), 13-6 (5.0 g, 25 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 13-7 (8.5 g, 77% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 71.08; H, 4.36; N, 6.38; Measured C, 71.04; H, 4.38; N, 6.31. Mass spectrometry: Theoretical 438.07; Measured 438.0 (M+).

[0250] Under an argon atmosphere, 13-7 (7.9 g, 18 mmol), 13-8 (5.4 g, 18 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 13-9 (8.4 g, 76% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 78.05; H, 4.42; N, 4.55 (test value). Mass spectrometry: Theoretical 614.14, experimental 614.1 (M+).

[0251] Under an argon atmosphere, 13-9 (8.0 g, 13 mmol), pinacol diborate (8.9 g, 35 mmol), potassium acetate (3.4 g, 35 mmol), dioxane (120 mL), and Pd(dppf)Cl2 (0.5 g, 0.7 mmol) were added to a 250 mL round-bottom flask and heated to reflux for 12 hours. After the reaction was complete, the mixture was cooled, the solvent was removed, and the product was hydrolyzed with an aqueous sodium hydroxide solution. The product was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain compound 13-10 (6.2 g, 82% yield). Elemental analysis: Theoretical C, 82.76; H, 5.04; N, 4.83; Measured C, 82.70; H, 5.09; N, 4.88. Mass spectrometry: Theoretical 580.23; Measured 580.2 (M+).

[0252] Under an argon atmosphere, 13-10 (5.8 g, 10 mmol), 13-11 (1.6 g, 10 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound H-28 (4.8 g, 79% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 90.16; H, 5.26; N, 4.57; Measured C, 90.11; H, 5.25; N, 4.54. Mass spectrometry: Theoretical 612.26; Measured 612.2 (M+).

[0253] Example 14

[0254] The reaction is as follows:

[0255]

[0256] Under an argon atmosphere, 14-1 (12.4 g, 40 mmol), 14-2 (7.4 g, 40 mmol), 15.2 g sodium metabisulfite (80 mmol), and N,N-dimethylformamide (100 mL) were added to a 250 mL round-bottom flask. The mixture was heated and stirred at 100 °C for 10 hours. After the reaction solution cooled to room temperature, it was poured into cold water and extracted three times with ethyl acetate (3 × 50 mL). The organic phase was separated, and the product compound 14-3 (15.4 g, 81% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical value C, 48.03; H, 2.55; N, 5.90; Measured value C, 48.01; H, 2.55; N, 5.82. Mass spectrometry: Theoretical value 473.92; Measured value 473.9 (M+).

[0257] Under an argon atmosphere, 14-3 (15.2 g, 32 mmol), 14-4 (6.8 g, 32 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 14-5 (12.9 g, 78% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 72.24; H, 3.72; N, 5.44; Measured C, 72.21; H, 3.78; N, 5.46. Mass spectrometry: Theoretical 516.07; Measured 516.0 (M+).

[0258] Under an argon atmosphere, 14-5 (11.3 g, 22 mmol), 14-6 (6.6 g, 22 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 14-7 (11.4 g, 75% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 78.15; H, 3.94; N, 4.05 (test value). Mass spectrometry: Theoretical 690.13, experimental 690.1 (M+).

[0259] Under an argon atmosphere, 14-7 (10.7 g, 15.5 mmol), pinacol diborate (8.9 g, 35 mmol), potassium acetate (3.4 g, 35 mmol), dioxane (120 mL), and Pd(dppf)Cl2 (0.5 g, 0.7 mmol) were added to a 250 mL round-bottom flask and heated to reflux for 12 hours. After the reaction was complete, the mixture was cooled, the solvent was removed, and the product was hydrolyzed with an aqueous sodium hydroxide solution. The solution was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain compound 14-8 (8.1 g, 80% yield). Elemental analysis: Theoretical value C, 82.32; H, 4.45; N, 4.27; Measured value C, 82.34; H, 4.48; N, 4.24. Mass spectrometry: Theoretical value 656.23; Measured value 656.2 (M+).

[0260] Under an argon atmosphere, 14-8 (6.6 g, 10 mmol), 14-9 (2.4 g, 10 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound H-35 (6.1 g, 79% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 88.46; H, 5.86; N, 3.62; Measured C, 88.41; H, 5.86; N, 3.65. Mass spectrometry: Theoretical 773.34; Measured 773.3 (M+).

[0261] Example 15: The reaction is as follows:

[0262]

[0263] Under an argon atmosphere, 15-1 (8.5 g, 40 mmol), 15-2 (14.7 g, 80 mmol), 19.0 g sodium metabisulfite (100 mmol), and N,N-dimethylformamide (140 mL) were added to a 250 mL round-bottom flask, and the mixture was heated and stirred at 100 °C for 10 hours. After the reaction solution cooled to room temperature, it was poured into cold water and extracted three times with ethyl acetate (3 × 50 mL). The organic phase was separated, and the product compound 15-3 (16.5 g, 76% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical value C, 70.99; H, 3.91; N, 10.35; Measured value C, 70.91; H, 3.90; N, 10.34. Mass spectrometry: Theoretical value 540.09; Measured value 540.0 (M+).

[0264] Under an argon atmosphere, 15-3 (15.7 g, 29 mmol), 15-4 (8.7 g, 29 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 15-5 (16.0 g, 77% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 76.99; H, 4.07; N, 7.81; Measured C, 76.94; H, 4.01; N, 7.88. Mass spectrometry: Theoretical 718.16; Measured 718.1 (M+).

[0265] Under an argon atmosphere, 15-5 (15.1 g, 21 mmol), pinacol diborate (8.9 g, 35 mmol), potassium acetate (3.4 g, 35 mmol), dioxane (120 mL), and Pd(dppf)Cl2 (0.5 g, 0.7 mmol) were added to a 250 mL round-bottom flask and heated to reflux for 12 hours. After the reaction was complete, the mixture was cooled, the solvent was removed, and the product was hydrolyzed with an aqueous sodium hydroxide solution. The solution was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain compound 15-6 (10.8 g, 75% yield). Elemental analysis: Theoretical C, 80.94; H, 4.58; N, 8.21 (test value). Mass spectrometry: Theoretical 682.25, experimental 682.2 (M+).

[0266] Under an argon atmosphere, 15-6 (10.2 g, 15 mmol), 15-7 (4.2 g, 15 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound H-36 (9.8 g, 78% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical value C, 88.54; H, 4.79; N, 6.66; Measured value C, 88.57; H, 4.74; N, 6.69. Mass spectrometry: Theoretical value 840.33; Measured value 840.3 (M+).

[0267] Example 16

[0268] The reaction is as follows:

[0269]

[0270] Under an argon atmosphere, 16-1 (12.4 g, 40 mmol), 16-2 (7.4 g, 40 mmol), 15.2 g sodium metabisulfite (80 mmol), and N,N-dimethylformamide (100 mL) were added to a 250 mL round-bottom flask. The mixture was heated and stirred at 100 °C for 10 hours. After the reaction solution cooled to room temperature, it was poured into cold water and extracted three times with ethyl acetate (3 × 50 mL). The organic phase was separated, and the product compound 16-3 (16.0 g, 84% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical value C, 48.03; H, 2.55; N, 5.90; Measured value C, 48.01; H, 2.58; N, 5.85. Mass spectrometry: Theoretical value 473.92; Measured value 473.9 (M+).

[0271] Under an argon atmosphere, 16-3 (15.2 g, 32 mmol), 16-4 (5.5 g, 32 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 16-5 (12.0 g, 79% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 73.27; H, 4.03; N, 5.89; Measured C, 73.20; H, 4.03; N, 5.88. Mass spectrometry: Theoretical 474.07; Measured 474.0 (M+).

[0272] Under an argon atmosphere, 16-5 (6.7 g, 14 mmol), 16-6 (4.2 g, 14 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 16-7 (7.1 g, 78% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 79.26; H, 4.18; N, 4.30; Measured C, 79.24; H, 4.19; N, 4.38. Mass spectrometry: Theoretical 650.14; Measured 650.1 (M+).

[0273] Under an argon atmosphere, 16-7 (6.5 g, 10 mmol), pinacol diborate (8.9 g, 35 mmol), potassium acetate (3.4 g, 35 mmol), dioxane (120 mL), and Pd(dppf)Cl2 (0.5 g, 0.7 mmol) were added to a 250 mL round-bottom flask and heated to reflux for 12 hours. After the reaction was complete, the mixture was cooled, the solvent was removed, and the product was hydrolyzed with an aqueous sodium hydroxide solution. The solution was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to give compound 16-8 (5.2 g, 85% yield). Elemental analysis: Theoretical C, 83.77; H, 4.74; N, 4.54; Measured C, 83.77; H, 4.74; N, 4.54. Mass spectrometry: Theoretical 616.23; Measured 616.2 (M+).

[0274] Under an argon atmosphere, 16-8 (4.9 g, 8 mmol), 16-5 (3.8 g, 8 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound H-40 (5.5 g, 71% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical value C, 89.41; H, 4.79; N, 5.79; Measured value C, 89.45; H, 4.79; N, 5.78. Mass spectrometry: Theoretical value 966.37; Measured value 966.3 (M+).

[0275] Example 17

[0276] The reaction is as follows:

[0277]

[0278] Under an argon atmosphere, 17-1 (12.4 g, 40 mmol), 17-2 (7.4 g, 40 mmol), 15.2 g sodium metabisulfite (80 mmol), and N,N-dimethylformamide (100 mL) were added to a 250 mL round-bottom flask. The mixture was heated and stirred at 100 °C for 10 hours. After the reaction solution cooled to room temperature, it was poured into cold water and extracted three times with ethyl acetate (3 × 50 mL). The organic phase was separated, and the product compound 17-3 (15.4 g, 81% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical value C, 48.03; H, 2.55; N, 5.90; Measured value C, 48.02; H, 2.50; N, 5.88. Mass spectrometry: Theoretical value 473.92; Measured value 473.9 (M+).

[0279] Under an argon atmosphere, 17-3 (14.7 g, 31 mmol), 17-4 (1.9 g, 31 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 17-5 (8.8 g, 78% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 66.13; H, 4.16; N, 7.71; Measured C, 66.11; H, 4.16; N, 7.78. Mass spectrometry: Theoretical 362.04; Measured 362.0 (M+).

[0280] Under an argon atmosphere, 17-5 (8.0 g, 22 mmol), 17-6 (6.6 g, 22 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 17-7 (8.9 g, 75% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 75.50; H, 4.30; N, 5.19 (test value). Mass spectrometry: Theoretical 538.10, experimental 538.1 (M+).

[0281] Under an argon atmosphere, 17-7 (8.1 g, 15 mmol), pinacol diborate (8.9 g, 35 mmol), potassium acetate (3.4 g, 35 mmol), dioxane (120 mL), and Pd(dppf)Cl2 (0.5 g, 0.7 mmol) were added to a 250 mL round-bottom flask and heated to reflux for 12 hours. After the reaction was complete, the mixture was cooled, the solvent was removed, and the product was hydrolyzed with an aqueous sodium hydroxide solution. The solution was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain compound 17-8 (6.2 g, 82% yield). Elemental analysis: Theoretical value C, 80.96; H, 5.00; N, 5.55; Measured value C, 80.95; H, 5.00; N, 5.57. Mass spectrometry: Theoretical value 504.20; Measured value 504.2 (M+).

[0282] Under an argon atmosphere, 17-8 (5.5 g, 11 mmol), 17-9 (1.8 g, 11 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound H-44 (4.4 g, 74% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 88.69; H, 6.14; N, 5.17; Measured C, 88.72; H, 6.10; N, 5.11. Mass spectrometry: Theoretical 541.26; Measured 541.2 (M+).

[0283] Example 18

[0284] The reaction is as follows:

[0285]

[0286] Under an argon atmosphere, 13.6 g (40 mmol) of 18-1, 14.7 g (80 mmol) of 18-2, 19.0 g of sodium metabisulfite (100 mmol) and 140 mL of N,N-dimethylformamide (140 mL) were added to a 250 mL round-bottom flask. The mixture was heated and stirred at 100 °C for 10 hours. After the reaction solution cooled to room temperature, it was poured into cold water and extracted three times with ethyl acetate (3 × 50 mL). The organic phase was separated, and the product compound 18-3 (20.3 g, 76% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical value C, 57.59; H, 3.02; N, 8.40; Measured value C, 57.51; H, 3.00; N, 8.24. Mass spectrometry: Theoretical value 665.99; Measured value 665.9 (M+).

[0287] Under an argon atmosphere, 18-3 (18.7 g, 28 mmol), 18-4 (3.4 g, 28 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 18-5 (13.5 g, 78% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 71.85; H, 3.91; N, 11.32; Measured C, 71.87; H, 3.90; N, 11.30. Mass spectrometry: Theoretical 617.12; Measured 617.1 (M+).

[0288] Under an argon atmosphere, 18-5 (12.4 g, 20 mmol), 18-6 (4.0 g, 20 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 18-7 (10.3 g, 74% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 74.35; H, 4.06; N, 10.08; Measured C, 74.31; H, 4.00; N, 10.12. Mass spectrometry: Theoretical 693.15; Measured 693.1 (M+).

[0289] Under an argon atmosphere, 18-7 (9.7 g, 14 mmol), 18-8 (4.2 g, 14 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 18-9 (9.6 g, 79% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 78.62; H, 4.17; N, 8.04; Measured C, 78.60; H, 4.19; N, 8.07. Mass spectrometry: Theoretical 869.22; Measured 869.2 (M+).

[0290] Under an argon atmosphere, 18-9 (9.1 g, 10.5 mmol), pinacol diborate (8.9 g, 35 mmol), potassium acetate (3.4 g, 35 mmol), dioxane (120 mL), and Pd(dppf)Cl2 (0.5 g, 0.7 mmol) were added to a 250 mL round-bottom flask and heated to reflux for 12 hours. After the reaction was complete, the mixture was cooled, the solvent was removed, and hydrolysis was performed with an aqueous sodium hydroxide solution. The product was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain compound 18-10 (7.4 g, 82% yield). Elemental analysis: Theoretical C, 81.92; H, 4.58; N, 8.38; Measured C, 81.91; H, 4.52; N, 8.38. Mass spectrometry: Theoretical 835.31; Measured 835.3 (M+).

[0291] Under an argon atmosphere, 18-10 (6.7 g, 8 mmol), 18-11 (1.7 g, 8 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound H-48 (5.4 g, 72% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 87.78; H, 4.80; N, 7.42; Measured C, 87.79; H, 4.82; N, 7.47. Mass spectrometry: Theoretical 943.37; Measured 943.3 (M+).

[0292] Example 19

[0293] The reaction is as follows:

[0294]

[0295] Under an argon atmosphere, 19-1 (12.4 g, 40 mmol), 19-2 (7.4 g, 40 mmol), 15.2 g sodium metabisulfite (80 mmol), and N,N-dimethylformamide (100 mL) were added to a 250 mL round-bottom flask. The mixture was heated and stirred at 100 °C for 10 hours. After the reaction solution cooled to room temperature, it was poured into cold water and extracted three times with ethyl acetate (3 × 50 mL). The organic phase was separated, and the product compound 19-3 (14.6 g, 77% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical value C, 48.03; H, 2.55; N, 5.90; Measured value C, 48.00; H, 2.55; N, 5.84. Mass spectrometry: Theoretical value 473.92; Measured value 473.9 (M+).

[0296] Under an argon atmosphere, 19-3 (14.3 g, 30 mmol), 19-4 (6.4 g, 30 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 19-5 (11.8 g, 76% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 72.24; H, 3.72; N, 5.44; Measured C, 72.21; H, 3.77; N, 5.44. Mass spectrometry: Theoretical 516.07; Measured 516.0 (M+).

[0297] Under an argon atmosphere, 19-5 (10.8 g, 21 mmol), 19-6 (6.3 g, 21 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 19-7 (10.9 g, 75% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 78.15; H, 3.94; N, 4.05; Measured C, 78.11; H, 3.95; N, 4.07. Mass spectrometry: Theoretical 690.13; Measured 690.1 (M+).

[0298] Under an argon atmosphere, 19-7 (10.4 g, 15 mmol), pinacol diborate (8.9 g, 35 mmol), potassium acetate (3.4 g, 35 mmol), dioxane (120 mL), and Pd(dppf)Cl2 (0.5 g, 0.7 mmol) were added to a 250 mL round-bottom flask and heated to reflux for 12 hours. After the reaction was complete, the mixture was cooled, the solvent was removed, and the product was hydrolyzed with an aqueous sodium hydroxide solution. The solution was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain compound 19-8 (8.0 g, 81% yield). Elemental analysis: Theoretical value C, 82.32; H, 4.45; N, 4.27; Measured value C, 82.32; H, 4.45; N, 4.27. Mass spectrometry: Theoretical value 656.23; Measured value 656.2 (M+).

[0299] Under an argon atmosphere, 19-8 (6.6 g, 10 mmol), 19-9 (1.6 g, 10 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound H-49 (5.1 g, 73% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical value C, 88.28; H, 5.37; N, 4.04; Measured value C, 88.28; H, 5.37; N, 4.04. Mass spectrometry: Theoretical value 693.28; Measured value 693.2 (M+).

[0300] Example 20

[0301] The reaction is as follows:

[0302]

[0303] Under an argon atmosphere, 20-1 (12.4 g, 40 mmol), 20-2 (7.4 g, 40 mmol), 15.2 g sodium metabisulfite (80 mmol), and N,N-dimethylformamide (100 mL) were added to a 250 mL round-bottom flask. The mixture was heated and stirred at 100 °C for 10 hours. After the reaction solution cooled to room temperature, it was poured into cold water and extracted three times with ethyl acetate (3 × 50 mL). The organic phase was separated, and the product compound 20-3 (14.6 g, 77% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical value C, 48.03; H, 2.55; N, 5.90; Measured value C, 48.02; H, 2.59; N, 5.89. Mass spectrometry: Theoretical value 473.92; Measured value 473.9 (M+).

[0304] Under an argon atmosphere, 20-3 (14.3 g, 30 mmol), 20-4 (3.7 g, 30 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 20-5 (9.7 g, 76% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 70.60; H, 4.03; N, 6.59; Measured C, 70.60; H, 4.03; N, 6.59. Mass spectrometry: Theoretical 426.06; Measured 426.0 (M+).

[0305] Under an argon atmosphere, 20-5 (8.9 g, 21 mmol), 20-6 (4.2 g, 21 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 20-7 (8.0 g, 76% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 74.26; H, 4.22; N, 5.59; Measured C, 74.24; H, 4.28; N, 5.58. Mass spectrometry: Theoretical 500.09; Measured 500.0 (M+).

[0306] Under an argon atmosphere, 20-7 (7.5 g, 15 mmol), 20-8 (4.5 g, 15 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 20-9 (7.7 g, 76% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 79.76; H, 4.31; N, 4.13 (test value). Mass spectrometry: Theoretical 676.15, experimental 676.1 (M+).

[0307] Under an argon atmosphere, 20-9 (7.1 g, 10.5 mmol), pinacol diborate (8.9 g, 35 mmol), potassium acetate (3.4 g, 35 mmol), dioxane (120 mL), and Pd(dppf)Cl2 (0.5 g, 0.7 mmol) were added to a 250 mL round-bottom flask and heated to reflux for 12 hours. After the reaction was complete, the mixture was cooled, the solvent was removed, and the product was hydrolyzed with an aqueous sodium hydroxide solution. The product was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain compound 20-10 (5.5 g, 82% yield). Elemental analysis: Theoretical C, 84.12; H, 4.86; N, 4.36; Measured C, 84.17; H, 4.84; N, 4.35. Mass spectrometry: Theoretical 642.25; Measured 642.2 (M+).

[0308] Under an argon atmosphere, 20-10 (5.1 g, 8 mmol), 20-11 (1.3 g, 8 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound H-51 (4.0 g, 74% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical value C, 90.77; H, 5.08; N, 4.15; Measured value C, 90.71; H, 5.11; N, 4.10. Mass spectrometry: Theoretical value 674.27; Measured value 674.2 (M+).

[0309] Example 21

[0310] The reaction is as follows:

[0311]

[0312] Under an argon atmosphere, 21-1 (12.4 g, 40 mmol), 21-2 (7.4 g, 40 mmol), 15.2 g sodium metabisulfite (80 mmol), and N,N-dimethylformamide (100 mL) were added to a 250 mL round-bottom flask. The mixture was heated and stirred at 100 °C for 10 hours. After the reaction solution cooled to room temperature, it was poured into cold water and extracted three times with ethyl acetate (3 × 50 mL). The organic phase was separated, and the product compound 21-3 (14.8 g, 78% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical value C, 48.03; H, 2.55; N, 5.90; Measured value C, 48.01; H, 2.55; N, 5.84. Mass spectrometry: Theoretical value 473.92; Measured value 473.9 (M+).

[0313] Under an argon atmosphere, 21-3 (14.3 g, 30 mmol), 21-4 (3.9 g, 30 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 21-5 (9.8 g, 76% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 69.77; H, 5.15; N, 6.51; Measured C, 69.77; H, 5.15; N, 6.51. Mass spectrometry: Theoretical 429.09; Measured 429.0 (M+).

[0314] Under an argon atmosphere, 21-5 (8.6 g, 20 mmol), 21-6 (6.0 g, 20 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 21-7 (8.0 g, 79% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 73.52; H, 5.17; N, 5.53; Measured C, 73.49; H, 5.15; N, 5.50. Mass spectrometry: Theoretical 505.12; Measured 505.1 (M+).

[0315] Under an argon atmosphere, 21-7 (7.6 g, 15 mmol), 21-8 (4.5 g, 15 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 21-9 (7.6 g, 74% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 79.17; H, 5.02; N, 4.10; Measured C, 79.20; H, 5.05; N, 4.10. Mass spectrometry: Theoretical 681.18; Measured 681.1 (M+).

[0316] Under an argon atmosphere, 21-9 (6.8 g, 10 mmol), pinacol diborate (8.9 g, 35 mmol), potassium acetate (3.4 g, 35 mmol), dioxane (120 mL), and Pd(dppf)Cl2 (0.5 g, 0.7 mmol) were added to a 250 mL round-bottom flask and heated to reflux for 12 hours. After the reaction was complete, the mixture was cooled, the solvent was removed, and the product was hydrolyzed with an aqueous sodium hydroxide solution. The product was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain compound 21-10 (5.1 g, 79% yield). Elemental analysis: Theoretical C, 83.46; H, 5.60; N, 4.33; Measured C, 83.44; H, 5.66; N, 4.28. Mass spectrometry: Theoretical 647.28; Measured 647.2 (M+).

[0317] Under an argon atmosphere, 21-10 (4.5 g, 7 mmol), 21-11 (1.1 g, 7 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound H-52 (3.5 g, 73% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical value C, 89.44; H, 6.47; N, 4.09; Measured value C, 89.41; H, 6.42; N, 4.00. Mass spectrometry: Theoretical value 684.33; Measured value 684.33 (M+).

[0318] Example 22

[0319] The reaction is as follows:

[0320]

[0321] Under an argon atmosphere, 22-1 (12.4 g, 40 mmol), 22-2 (7.4 g, 40 mmol), 15.2 g sodium metabisulfite (80 mmol), and N,N-dimethylformamide (100 mL) were added to a 250 mL round-bottom flask. The mixture was heated and stirred at 100 °C for 10 hours. After the reaction solution cooled to room temperature, it was poured into cold water and extracted three times with ethyl acetate (3 × 50 mL). The organic phase was separated, and the product compound 22-3 (14.4 g, 76% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical value C, 48.03; H, 2.55; N, 5.90; Measured value C, 48.02; H, 2.55; N, 5.83. Mass spectrometry: Theoretical value 473.92; Measured value 473.9 (M+).

[0322] Under an argon atmosphere, 22-3 (13.3 g, 28 mmol), 22-4 (5.9 g, 28 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 22-5 (11.4 g, 79% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 72.24; H, 3.72; N, 5.44; Measured C, 72.20; H, 3.72; N, 5.46. Mass spectrometry: Theoretical 516.07; Measured 516.0 (M+).

[0323] Under an argon atmosphere, 22-5 (10.8 g, 21 mmol), 22-6 (4.2 g, 21 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 22-7 (9.1 g, 73% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 75.13; H, 3.92; N, 4.74; Measured C, 75.14; H, 3.90; N, 4.76. Mass spectrometry: Theoretical 590.10; Measured 590.1 (M+).

[0324] Under an argon atmosphere, 22-7 (8.3 g, 14 mmol), 22-8 (4.2 g, 14 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 22-9 (8.2 g, 76% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 79.79; H, 4.07; N, 3.65; Measured C, 79.82; H, 4.02; N, 3.67. Mass spectrometry: Theoretical 766.16; Measured 766.1 (M+).

[0325] Under an argon atmosphere, 22-9 (7.3 g, 9.5 mmol), pinacol diborate (8.9 g, 35 mmol), potassium acetate (3.4 g, 35 mmol), dioxane (120 mL), and Pd(dppf)Cl2 (0.5 g, 0.7 mmol) were added to a 250 mL round-bottom flask and heated to reflux for 12 hours. After the reaction was complete, the mixture was cooled, the solvent was removed, and the product was hydrolyzed with an aqueous sodium hydroxide solution. The solution was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain compound 22-10 (5.5 g, 79% yield). Elemental analysis: Theoretical C, 83.61; H, 4.54; N, 3.82; Measured C, 83.64; H, 4.58; N, 3.81. Mass spectrometry: Theoretical 732.26; Measured 732.2 (M+).

[0326] Under an argon atmosphere, 22-10 (5.1 g, 7 mmol), 22-11 (1.1 g, 7 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound H-54 (3.9 g, 72% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 88.92; H, 5.37; N, 3.64; Measured C, 88.97; H, 5.32; N, 3.60. Mass spectrometry: Theoretical 769.31; Measured 769.3 (M+).

[0327] Example 23

[0328] The reaction is as follows:

[0329]

[0330] Under an argon atmosphere, 23-1 (13.6 g, 40 mmol), 23-2 (14.7 g, 80 mmol), 19.0 g sodium metabisulfite (100 mmol), and N,N-dimethylformamide (140 mL) were added to a 250 mL round-bottom flask, and the mixture was heated and stirred at 100 °C for 10 hours. After the reaction solution cooled to room temperature, it was poured into cold water and extracted three times with ethyl acetate (3 × 50 mL). The organic phase was separated, and the product compound 23-3 (20.8 g, 78% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical value C, 57.59; H, 3.02; N, 8.40; Measured value C, 57.51; H, 3.02; N, 8.24. Mass spectrometry: Theoretical value 665.99; Measured value 665.9 (M+).

[0331] Under an argon atmosphere, 23-3 (20.0 g, 30 mmol), 23-4 (5.9 g, 30 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 23-5 (15.8 g, 76% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 76.19; H, 4.21; N, 8.08; Measured C, 76.15; H, 4.20; N, 8.14. Mass spectrometry: Theoretical 694.16; Measured 694.1 (M+).

[0332] Under an argon atmosphere, 23-5 (14.6 g, 21 mmol), 23-6 (4.2 g, 21 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 23-7 (12.1 g, 75% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 78.02; H, 4.32; N, 7.28; Measured C, 78.09; H, 4.28; N, 7.28. Mass spectrometry: Theoretical 768.19; Measured 768.1 (M+).

[0333] Under an argon atmosphere, 23-7 (11.5 g, 15 mmol), 23-8 (4.5 g, 15 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 23-9 (11.2 g, 79% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 81.26; H, 4.37; N, 5.92; Measured C, 81.21; H, 4.37; N, 5.90. Mass spectrometry: Theoretical 944.25; Measured 944.2 (M+).

[0334] Under an argon atmosphere, 23-9 (10.4 g, 11 mmol), pinacol diborate (8.9 g, 35 mmol), potassium acetate (3.4 g, 35 mmol), dioxane (120 mL), and Pd(dppf)Cl2 (0.5 g, 0.7 mmol) were added to a 250 mL round-bottom flask and heated to reflux for 12 hours. After the reaction was complete, the mixture was cooled, the solvent was removed, and the product was hydrolyzed with an aqueous sodium hydroxide solution. The product was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain compound 23-10 (8.1 g, 81% yield). Elemental analysis: Theoretical C, 84.39; H, 4.76; N, 6.15; Measured C, 84.42; H, 4.78; N, 6.21. Mass spectrometry: Theoretical 910.35; Measured 910.3 (M+).

[0335] Under an argon atmosphere, 23-10 (7.3 g, 8 mmol), 23-11 (1.9 g, 8 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound H-55 (5.9 g, 72% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 89.56; H, 4.94; N, 5.50; Measured C, 89.51; H, 4.90; N, 5.58. Mass spectrometry: Theoretical 10¹⁸.40; Measured 10¹⁸.4 (M+).

[0336] Example 24

[0337] The reaction is as follows:

[0338]

[0339] Under an argon atmosphere, 24-1 (13.6 g, 40 mmol), 24-2 (14.7 g, 80 mmol), 19.0 g sodium metabisulfite (100 mmol), and N,N-dimethylformamide (140 mL) were added to a 250 mL round-bottom flask, and the mixture was heated and stirred at 100 °C for 10 hours. After the reaction solution cooled to room temperature, it was poured into cold water and extracted three times with ethyl acetate (3 × 50 mL). The organic phase was separated, and the product compound 24-3 (20.3 g, 76% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical value C, 57.59; H, 3.02; N, 8.40; Measured value C, 57.51; H, 3.09; N, 8.22. Mass spectrometry: Theoretical value 665.99; Measured value 665.9 (M+).

[0340] Under an argon atmosphere, 24-3 (18.7 g, 28 mmol), 24-4 (7.8 g, 28 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 24-5 (16.0 g, 74% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 73.06; H, 3.91; N, 12.69; Measured C, 73.01; H, 3.94; N, 12.62. Mass spectrometry: Theoretical 771.17; Measured 771.1 (M+).

[0341] Under an argon atmosphere, 24-5 (15.5 g, 20 mmol), 24-6 (4.0 g, 20 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 24-7 (12.4 g, 73% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 75.00; H, 4.04; N, 11.55; Measured C, 75.09; H, 4.00; N, 11.55. Mass spectrometry: Theoretical 847.21; Measured 847.2 (M+).

[0342] Under an argon atmosphere, 24-7 (11.9 g, 14 mmol), 24-8 (4.2 g, 14 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 24-9 (11.2 g, 78% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 78.51; H, 4.13; N, 9.57; Measured C, 78.54; H, 4.16; N, 9.52. Mass spectrometry: Theoretical 1023.27; Measured 1023.2 (M+).

[0343] Under an argon atmosphere, 24-9 (10.8 g, 10.5 mmol), pinacol diborate (8.9 g, 35 mmol), potassium acetate (3.4 g, 35 mmol), dioxane (120 mL), and Pd(dppf)Cl2 (0.5 g, 0.7 mmol) were added to a 250 mL round-bottom flask and heated to reflux for 12 hours. After the reaction was complete, the mixture was cooled, the solvent was removed, and the product was hydrolyzed with an aqueous sodium hydroxide solution. The product was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain compound 24-10 (8.2 g, 79% yield). Elemental analysis: Theoretical C, 81.29; H, 4.48; N, 9.90; Measured C, 81.24; H, 4.52; N, 9.90. Mass spectrometry: Theoretical 989.36; Measured 989.3 (M+).

[0344] Under an argon atmosphere, 24-10 (6.9 g, 7 mmol), 24-11 (1.1 g, 7 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound H-56 (5.2 g, 73% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 85.77; H, 4.63; N, 9.59; Measured C, 85.74; H, 4.60; N, 9.63. Mass spectrometry: Theoretical 1021.39; Measured 1021.3 (M+).

[0345] Example 25

[0346] The reaction is as follows:

[0347]

[0348] Under an argon atmosphere, 25-1 (12.4 g, 40 mmol), 25-2 (7.4 g, 40 mmol), 15.2 g sodium metabisulfite (80 mmol), and N,N-dimethylformamide (100 mL) were added to a 250 mL round-bottom flask. The mixture was heated and stirred at 100 °C for 10 hours. After the reaction solution cooled to room temperature, it was poured into cold water and extracted three times with ethyl acetate (3 × 50 mL). The organic phase was separated, and the product compound 25-3 (14.2 g, 75% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical value C, 48.03; H, 2.55; N, 5.90; Measured value C, 48.00; H, 2.55; N, 5.87. Mass spectrometry: Theoretical value 473.92; Measured value 473.9 (M+).

[0349] Under an argon atmosphere, 25-3 (13.3 g, 28 mmol), 25-4 (1.7 g, 28 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 25-5 (7.7 g, 76% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 66.13; H, 4.16; N, 7.71; Measured C, 66.08; H, 4.12; N, 7.76. Mass spectrometry: Theoretical 362.04; Measured 362.0 (M+).

[0350] Under an argon atmosphere, 25-5 (7.2 g, 20 mmol), 25-6 (6.0 g, 20 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 25-7 (8.3 g, 77% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 75.70; H, 4.30; N, 5.19; Measured C, 75.75; H, 4.28; N, 5.19. Mass spectrometry: Theoretical 538.10; Measured 538.1 (M+).

[0351] Under an argon atmosphere, 25-7 (7.8 g, 14.5 mmol), pinacol diborate (8.9 g, 35 mmol), potassium acetate (3.4 g, 35 mmol), dioxane (120 mL), and Pd(dppf)Cl2 (0.5 g, 0.7 mmol) were added to a 250 mL round-bottom flask and heated to reflux for 12 hours. After the reaction was complete, the mixture was cooled, the solvent was removed, and the product was hydrolyzed with an aqueous sodium hydroxide solution. The solution was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain compound 25-8 (5.6 g, 76% yield). Elemental analysis: Theoretical C, 80.96; H, 5.00; N, 5.55; Measured C, 80.98; H, 5.04; N, 5.57. Mass spectrometry: Theoretical 504.20; Measured 504.2 (M+).

[0352] Under an argon atmosphere, 25-8 (5.0 g, 10 mmol), 25-9 (2.3 g, 10 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound H-58 (4.7 g, 75% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical value C, 90.21; H, 5.32; N, 4.48; Measured value C, 90.28; H, 5.30; N, 4.48. Mass spectrometry: Theoretical value 625.26; Measured value 625.2 (M+).

[0353] Example 26

[0354] The reaction is as follows:

[0355]

[0356] Under an argon atmosphere, 26-1 (13.6 g, 40 mmol), 26-2 (14.7 g, 80 mmol), 19.0 g sodium metabisulfite (100 mmol), and N,N-dimethylformamide (140 mL) were added to a 250 mL round-bottom flask, and the mixture was heated and stirred at 100 °C for 10 hours. After the reaction solution cooled to room temperature, it was poured into cold water and extracted three times with ethyl acetate (3 × 50 mL). The organic phase was separated, and the product compound 26-3 (20.5 g, 77% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical value C, 57.59; H, 3.02; N, 8.40; Measured value C, 57.51; H, 3.00; N, 8.27. Mass spectrometry: Theoretical value 665.99; Measured value 665.9 (M+).

[0357] Under an argon atmosphere, 26-3 (20.0 g, 30 mmol), 26-4 (3.8 g, 30 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 26-5 (13.4 g, 72% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 73.31; H, 4.86; N, 9.00; Measured C, 73.39; H, 4.82; N, 9.04. Mass spectrometry: Theoretical 621.16; Measured 621.1 (M+).

[0358] Under an argon atmosphere, 26-5 (12.4 g, 20 mmol), 26-6 (6.0 g, 20 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 26-7 (11.5 g, 72% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 78.19; H, 4.79; N, 7.01; Measured C, 78.08; H, 4.72; N, 7.01. Mass spectrometry: Theoretical 797.22; Measured 797.2 (M+).

[0359] Under an argon atmosphere, 26-7 (10.8 g, 13.5 mmol), pinacol diborate (8.9 g, 35 mmol), potassium acetate (3.4 g, 35 mmol), dioxane (120 mL), and Pd(dppf)Cl2 (0.5 g, 0.7 mmol) were added to a 250 mL round-bottom flask and heated to reflux for 12 hours. After the reaction was complete, the mixture was cooled, the solvent was removed, and the product was hydrolyzed with an aqueous sodium hydroxide solution. The product was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain compound 26-8 (8.0 g, 78% yield). Elemental analysis: Theoretical C, 81.78; H, 5.28; N, 7.34; Measured C, 81.80; H, 5.28; N, 7.32. Mass spectrometry: Theoretical 763.32; Measured 763.3 (M+).

[0360] Under an argon atmosphere, 26-8 (6.1 g, 8 mmol), 26-9 (1.3 g, 8 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound H-60 ​​(4.6 g, 72% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 86.97; H, 6.04; N, 6.99; Measured C, 86.99; H, 6.04; N, 6.92. Mass spectrometry: Theoretical 800.37; Measured 800.3 (M+).

[0361] Example 27

[0362] The reaction is as follows:

[0363]

[0364] Under an argon atmosphere, 27-1 (12.4 g, 40 mmol), 27-2 (7.4 g, 40 mmol), 15.2 g sodium metabisulfite (80 mmol), and N,N-dimethylformamide (100 mL) were added to a 250 mL round-bottom flask. The mixture was heated and stirred at 100 °C for 10 hours. After the reaction solution cooled to room temperature, it was poured into cold water and extracted three times with ethyl acetate (3 × 50 mL). The organic phase was separated, and the product compound 27-3 (14.2 g, 75% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical value C, 48.03; H, 2.55; N, 5.90; Measured value C, 48.02; H, 2.56; N, 5.82. Mass spectrometry: Theoretical value 473.92; Measured value 473.9 (M+).

[0365] Under an argon atmosphere, 27-3 (13.3 g, 28 mmol), 27-4 (4.1 g, 28 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 27-5 (8.8 g, 74% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 70.60; H, 4.03; N, 6.59; Measured C, 70.64; H, 4.03; N, 6.59. Mass spectrometry: Theoretical 424.06; Measured 424.0 (M+).

[0366] Under an argon atmosphere, 27-5 (8.1 g, 19 mmol), 27-6 (5.7 g, 19 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 27-7 (8.3 g, 73% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 77.87; H, 4.19; N, 4.66; Measured C, 77.82; H, 4.22; N, 4.60. Mass spectrometry: Theoretical 600.12; Measured 600.1 (M+).

[0367] Under an argon atmosphere, 27-7 (7.2 g, 12 mmol), pinacol diborate (8.9 g, 35 mmol), potassium acetate (3.4 g, 35 mmol), dioxane (120 mL), and Pd(dppf)Cl2 (0.5 g, 0.7 mmol) were added to a 250 mL round-bottom flask and heated to reflux for 12 hours. After the reaction was complete, the mixture was cooled, the solvent was removed, and the product was hydrolyzed with an aqueous sodium hydroxide solution. The solution was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain compound 27-8 (5.4 g, 79% yield). Elemental analysis: Theoretical C, 82.69; H, 4.80; N, 4.95; Measured C, 82.69; H, 4.83; N, 4.91. Mass spectrometry: Theoretical 566.22; Measured 566.2 (M+).

[0368] Under an argon atmosphere, 27-8 (4.5 g, 8 mmol), 27-9 (1.9 g, 8 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound H-62 (4.1 g, 76% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical value C, 90.77; H, 5.08; N, 4.15; Measured value C, 90.77; H, 5.11; N, 4.10. Mass spectrometry: Theoretical value 674.27; Measured value 674.2 (M+).

[0369] Example 28

[0370] The reaction is as follows:

[0371]

[0372] Under an argon atmosphere, 28-1 (12.4 g, 40 mmol), 28-2 (7.4 g, 40 mmol), 15.2 g sodium metabisulfite (80 mmol), and N,N-dimethylformamide (100 mL) were added to a 250 mL round-bottom flask. The mixture was heated and stirred at 100 °C for 10 hours. After the reaction solution cooled to room temperature, it was poured into cold water and extracted three times with ethyl acetate (3 × 50 mL). The organic phase was separated, and the product compound 28-3 (14.4 g, 76% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical value C, 48.03; H, 2.55; N, 5.90; Measured value C, 48.01; H, 2.52; N, 5.80. Mass spectrometry: Theoretical value 473.92; Measured value 473.9 (M+).

[0373] Under an argon atmosphere, 28-3 (13.3 g, 28 mmol), 28-4 (3.6 g, 28 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 28-5 (9.3 g, 77% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 69.77; H, 5.15; N, 6.51; Measured C, 69.81; H, 5.15; N, 6.50. Mass spectrometry: Theoretical 429.09; Measured 429.0 (M+).

[0374] Under an argon atmosphere, 28-5 (5.6 g, 13 mmol), 28-6 (3.9 g, 13 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 28-7 (5.8 g, 74% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 77.22; H, 4.98; N, 4.62; Measured C, 77.20; H, 4.98; N, 4.64. Mass spectrometry: Theoretical 605.15; Measured 605.1 (M+).

[0375] Under an argon atmosphere, 28-7 (5.4 g, 9 mmol), pinacol diborate (8.9 g, 35 mmol), potassium acetate (3.4 g, 35 mmol), dioxane (120 mL), and Pd(dppf)Cl2 (0.5 g, 0.7 mmol) were added to a 250 mL round-bottom flask and heated to reflux for 12 hours. After the reaction was complete, the mixture was cooled, the solvent was removed, and the product was hydrolyzed with an aqueous sodium hydroxide solution. The solution was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain compound 28-8 (4.1 g, 79% yield). Elemental analysis: Theoretical C, 81.97; H, 5.64; N, 4.90; Measured C, 81.97; H, 5.60; N, 4.90. Mass spectrometry: Theoretical 571.25; Measured 571.2 (M+).

[0376] Under an argon atmosphere, 28-8 (3.4 g, 6 mmol), 28-5 (2.6 g, 6 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound H-65 (4.2 g, 80% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 87.64; H, 5.97; N, 6.39; Measured C, 87.68; H, 5.97; N, 6.35. Mass spectrometry: Theoretical 876.40; Measured 876.4 (M+).

[0377] Example 29

[0378] The reaction is as follows:

[0379]

[0380] Under an argon atmosphere, 29-1 (12.4 g, 40 mmol), 29-2 (7.4 g, 40 mmol), 15.2 g sodium metabisulfite (80 mmol), and N,N-dimethylformamide (100 mL) were added to a 250 mL round-bottom flask. The mixture was heated and stirred at 100 °C for 10 hours. After the reaction solution cooled to room temperature, it was poured into cold water and extracted three times with ethyl acetate (3 × 50 mL). The organic phase was separated, and the product compound 29-3 (14.8 g, 78% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical value C, 48.03; H, 2.55; N, 5.90; Measured value C, 48.08; H, 2.52; N, 5.79. Mass spectrometry: Theoretical value 473.92; Measured value 473.9 (M+).

[0381] Under an argon atmosphere, 29-3 (14.2 g, 30 mmol), 29-4 (7.9 g, 30 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 29-5 (12.9 g, 76% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 74.34; H, 3.74; N, 4.95; Measured C, 74.35; H, 3.76; N, 4.90. Mass spectrometry: Theoretical 564.08; Measured 564.0 (M+).

[0382] Under an argon atmosphere, 29-5 (11.3 g, 20 mmol), 29-6 (4.0 g, 20 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 29-7 (9.6 g, 75% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 76.76; H, 3.93; N, 4.37; Measured C, 76.78; H, 3.93; N, 4.32. Mass spectrometry: Theoretical 640.12; Measured 640.1 (M+).

[0383] Under an argon atmosphere, 29-7 (9.0 g, 14 mmol), 29-8 (4.2 g, 14 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 29-9 (8.2 g, 72% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 80.8; H, 4.07; N, 3.43; Measured C, 80.5; H, 4.01; N, 3.42. Mass spectrometry: Theoretical 816.18; Measured 816.1 (M+).

[0384] Under an argon atmosphere, 29-9 (7.3 g, 9 mmol), pinacol diborate (8.9 g, 35 mmol), potassium acetate (3.4 g, 35 mmol), dioxane (120 mL), and Pd(dppf)Cl2 (0.5 g, 0.7 mmol) were added to a 250 mL round-bottom flask and heated to reflux for 12 hours. After the reaction was complete, the mixture was cooled, the solvent was removed, and the product was hydrolyzed with an aqueous sodium hydroxide solution. The solution was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain compound 29-10 (5.7 g, 81% yield). Elemental analysis: Theoretical C, 84.40; H, 4.51; N, 3.58; Measured C, 84.42; H, 4.56; N, 3.58. Mass spectrometry: Theoretical 782.27; Measured 782.2 (M+).

[0385] Under an argon atmosphere, 29-10 (5.5 g, 7 mmol), 29-11 (1.1 g, 7 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound H-69 (4.2 g, 73% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 89.35; H, 5.28; N, 3.42; Measured C, 89.35; H, 5.26; N, 3.40. Mass spectrometry: Theoretical 819.33; Measured 819.3 (M+).

[0386] Example 30

[0387] The reaction is as follows:

[0388]

[0389] Under an argon atmosphere, (12.4 g, 40 mmol), (7.4 g, 40 mmol), 15.2 g sodium metabisulfite (80 mmol), and N,N-dimethylformamide (100 mL) were added to a 250 mL round-bottom flask. The mixture was heated and stirred at 100 °C for 10 hours. After the reaction solution cooled to room temperature, it was poured into cold water and extracted three times with ethyl acetate (3 × 50 mL). The organic phase was separated, and the product compound (15.2 g, 80% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical value C, 48.03; H, 2.55; N, 5.90; Measured value C, 48.02; H, 2.54; N, 5.80. Mass spectrometry: Theoretical value 473.92; Measured value 473.9 (M+).

[0390] Under an argon atmosphere, 30-3 (14.2 g, 30 mmol), 30-4 (6.4 g, 30 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 30-5 (11.7 g, 76% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 72.24; H, 3.72; N, 5.44; Measured C, 72.25; H, 3.70; N, 5.46. Mass spectrometry: Theoretical 514.07; Measured 514.0 (M+).

[0391] Under an argon atmosphere, 30-5 (10.8 g, 21 mmol), 30-6 (4.2 g, 21 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 30-7 (8.9 g, 72% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 75.13; H, 3.92; N, 4.74; Measured C, 75.10; H, 3.95; N, 4.74. Mass spectrometry: Theoretical 590.10; Measured 590.1 (M+).

[0392] Under an argon atmosphere, 30-7 (8.3 g, 14 mmol), 30-8 (4.2 g, 14 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 30-9 (8.2 g, 76% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 79.79; H, 4.07; N, 3.65; Measured C, 79.82; H, 4.07; N, 3.68. Mass spectrometry: Theoretical 766.16; Measured 766.1 (M+).

[0393] Under an argon atmosphere, 30-9 (7.7 g, 10 mmol), pinacol diborate (8.9 g, 35 mmol), potassium acetate (3.4 g, 35 mmol), dioxane (120 mL), and Pd(dppf)Cl2 (0.5 g, 0.7 mmol) were added to a 250 mL round-bottom flask and heated to reflux for 12 hours. After the reaction was complete, the mixture was cooled, the solvent was removed, and the product was hydrolyzed with an aqueous sodium hydroxide solution. The solution was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain compound 30-10 (5.8 g, 79% yield). Elemental analysis: Theoretical C, 83.61; H, 4.54; N, 3.82; Measured C, 83.60; H, 4.57; N, 3.82. Mass spectrometry: Theoretical 732.26; Measured 732.2 (M+).

[0394] Under an argon atmosphere, 30-10 (5.1 g, 7 mmol), 30-11 (1.1 g, 7 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound H-70 (4.0 g, 74% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 89.50; H, 4.74; N, 3.66; Measured C, 89.55; H, 4.76; N, 3.63. Mass spectrometry: Theoretical 764.28; Measured 764.2 (M+).

[0395] Example 31

[0396] The reaction is as follows:

[0397]

[0398] Under an argon atmosphere, 31-1 (13.6 g, 40 mmol), 31-2 (14.7 g, 80 mmol), 19.0 g sodium metabisulfite (100 mmol), and N,N-dimethylformamide (140 mL) were added to a 250 mL round-bottom flask, and the mixture was heated and stirred at 100 °C for 10 hours. After the reaction solution cooled to room temperature, it was poured into cold water and extracted three times with ethyl acetate (3 × 50 mL). The organic phase was separated, and the product compound 31-3 (21.0 g, 79% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical value C, 57.59; H, 3.02; N, 8.40; Measured value C, 57.54; H, 3.00; N, 8.28. Mass spectrometry: Theoretical value 665.99; Measured value 665.9 (M+).

[0399] Under an argon atmosphere, 31-3 (20.0 g, 30 mmol), 31-4 (3.8 g, 30 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 31-5 (13.8 g, 74% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 73.31; H, 4.86; N, 9.00; Measured C, 73.30; H, 4.84; N, 9.05. Mass spectrometry: Theoretical 621.16; Measured 621.1 (M+).

[0400] Under an argon atmosphere, 31-5 (13.0 g, 21 mmol), 31-6 (6.3 g, 21 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 31-7 (12.2 g, 73% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 78.19; H, 4.79; N, 7.01; Measured C, 78.22; H, 4.81; N, 7.05. Mass spectrometry: Theoretical 797.22; Measured 797.2 (M+).

[0401] Under an argon atmosphere, 31-7 (11.2 g, 14 mmol), pinacol diborate (8.9 g, 35 mmol), potassium acetate (3.4 g, 35 mmol), dioxane (120 mL), and Pd(dppf)Cl2 (0.5 g, 0.7 mmol) were added to a 250 mL round-bottom flask and heated to reflux for 12 hours. After the reaction was complete, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The product was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain compound 31-8 (8.7 g, 81% yield). Elemental analysis: Theoretical C, 81.78; H, 5.28; N, 7.34; Measured C, 81.82; H, 5.23; N, 7.30. Mass spectrometry: Theoretical 763.32; Measured 763.3 (M+).

[0402] Under an argon atmosphere, 31-8 (7.6 g, 10 mmol), 31-9 (2.4 g, 10 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound H-75 (6.7 g, 76% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 87.24; H, 6.40; N, 6.36; Measured C, 87.20; H, 6.45; N, 6.32. Mass spectrometry: Theoretical 880.43; Measured 880.4 (M+).

[0403] Example 32

[0404] The reaction is as follows:

[0405]

[0406] Under an argon atmosphere, 32-1 (13.6 g, 40 mmol), 32-2 (14.7 g, 80 mmol), 19.0 g sodium metabisulfite (100 mmol), and N,N-dimethylformamide (140 mL) were added to a 250 mL round-bottom flask. The mixture was heated and stirred at 100 °C for 10 hours. After the reaction solution cooled to room temperature, it was poured into cold water and extracted three times with ethyl acetate (3 × 50 mL). The organic phase was separated, and the product compound 32-3 (20.8 g, 78% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical value C, 57.59; H, 3.02; N, 8.40; Measured value C, 57.51; H, 3.00; N, 8.21. Mass spectrometry: Theoretical value 665.99; Measured value 665.9 (M+).

[0407] Under an argon atmosphere, 32-3 (20.0 g, 30 mmol), 32-4 (6.4 g, 30 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 32-5 (16.5 g, 78% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 74.68; H, 3.85; N, 7.92; Measured C, 74.71; H, 3.80; N, 7.96. Mass spectrometry: Theoretical 706.14; Measured 706.1 (M+).

[0408] Under an argon atmosphere, 32-5 (15.5 g, 22 mmol), 32-6 (6.6 g, 22 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 32-7 (14.4 g, 74% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 78.82; H, 3.99; N, 6.34; Measured C, 78.85; H, 3.94; N, 6.30. Mass spectrometry: Theoretical 882.20; Measured 882.2 (M+).

[0409] Under an argon atmosphere, 32-7 (13.2 g, 15 mmol), pinacol diborate (8.9 g, 35 mmol), potassium acetate (3.4 g, 35 mmol), dioxane (120 mL), and Pd(dppf)Cl2 (0.5 g, 0.7 mmol) were added to a 250 mL round-bottom flask and heated to reflux for 12 hours. After the reaction was complete, the mixture was cooled, the solvent was removed, and the product was hydrolyzed with an aqueous sodium hydroxide solution. The solution was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain compound 32-8 (9.5 g, 75% yield). Elemental analysis: Theoretical value C, 82.08; H, 4.39; N, 6.60; Measured value C, 82.05; H, 4.41; N, 6.62. Mass spectrometry: Theoretical value 848.30; Measured value 848.3 (M+).

[0410] Under an argon atmosphere, 32-8 (8.5 g, 10 mmol), 32-9 (1.6 g, 10 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound H-78 (6.7 g, 76% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical value C, 87.25; H, 4.58; N, 6.36; Measured value C, 87.21; H, 4.59; N, 6.32. Mass spectrometry: Theoretical value 880.32; Measured value 880.3 (M+).

[0411] Example 33

[0412] The reaction is as follows:

[0413]

[0414] Under an argon atmosphere, 33-1 (13.6 g, 40 mmol), 33-2 (14.7 g, 80 mmol), 19.0 g sodium metabisulfite (100 mmol), and N,N-dimethylformamide (140 mL) were added to a 250 mL round-bottom flask, and the mixture was heated and stirred at 100 °C for 10 hours. After the reaction solution cooled to room temperature, it was poured into cold water and extracted three times with ethyl acetate (3 × 50 mL). The organic phase was separated, and the product compound 33-3 (21.0 g, 79% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical value C, 57.59; H, 3.02; N, 8.40; Measured value C, 57.50; H, 3.08; N, 8.21. Mass spectrometry: Theoretical value 665.99; Measured value 665.9 (M+).

[0415] Under an argon atmosphere, 33-3 (20.0 g, 30 mmol), 33-4 (3.7 g, 30 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 33-5 (14.0 g, 76% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 73.91; H, 4.08; N, 9.07; Measured C, 73.90; H, 4.11; N, 9.02. Mass spectrometry: Theoretical 616.3; Measured 616.1 (M+).

[0416] Under an argon atmosphere, 33-5 (12.3 g, 20 mmol), 33-6 (4.0 g, 20 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 33-7 (10.2 g, 74% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 76.19; H, 4.21; N, 8.08; Measured C, 76.22; H, 4.20; N, 8.06. Mass spectrometry: Theoretical 692.16; Measured 692.1 (M+).

[0417] Under an argon atmosphere, 33-7 (9.7 g, 14 mmol), 33-8 (4.2 g, 14 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 33-9 (9.4 g, 77% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical value C, 80.09; H, 4.29; N, 6.44; Measured value C, 80.12; H, 4.22; N, 6.40. Mass spectrometry: Theoretical value 868.22; Measured value 868.2 (M+).

[0418] Under an argon atmosphere, 33-9 (8.7 g, 10 mmol), pinacol diborate (8.9 g, 35 mmol), potassium acetate (3.4 g, 35 mmol), dioxane (120 mL), and Pd(dppf)Cl2 (0.5 g, 0.7 mmol) were added to a 250 mL round-bottom flask and heated to reflux for 12 hours. After the reaction was complete, the mixture was cooled, the solvent was removed, and hydrolysis was performed with an aqueous sodium hydroxide solution. The product was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain compound 33-10 (6.6 g, 79% yield). Elemental analysis: Theoretical value C, 834.3; H, 4.71; N, 6.71; Measured value C, 834.8; H, 4.70; N, 6.75. Mass spectrometry: Theoretical value 834.32; Measured value 834.3 (M+).

[0419] Under an argon atmosphere, 33-10 (5.8 g, 7 mmol), 33-11 (1.6 g, 7 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound H-82 (4.9 g, 74% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 89.14; H, 4.92; N, 5.94; Measured C, 89.08; H, 4.92; N, 5.90. Mass spectrometry: Theoretical 942.37; Measured 942.3 (M+).

[0420] Example 34

[0421] The reaction is as follows:

[0422]

[0423] Under an argon atmosphere, 34-1 (13.6 g, 40 mmol), 34-2 (14.7 g, 80 mmol), 19.0 g sodium metabisulfite (100 mmol), and N,N-dimethylformamide (140 mL) were added to a 250 mL round-bottom flask, and the mixture was heated and stirred at 100 °C for 10 hours. After the reaction solution cooled to room temperature, it was poured into cold water and extracted three times with ethyl acetate (3 × 50 mL). The organic phase was separated, and the product compound 34-3 (20.8 g, 78% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical value C, 57.59; H, 3.02; N, 8.40; Measured value C, 57.51; H, 3.03; N, 8.24. Mass spectrometry: Theoretical value 665.99; Measured value 665.9 (M+).

[0424] Under an argon atmosphere, 34-3 (20.0 g, 30 mmol), 34-4 (1.8 g, 30 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 34-5 (12.6 g, 76% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 71.36; H, 4.17; N, 10.09; Measured C, 71.41; H, 4.13; N, 10.12. Mass spectrometry: Theoretical 554.11; Measured 554.1 (M+).

[0425] Under an argon atmosphere, 34-5 (11.6 g, 21 mmol), 34-6 (6.3 g, 21 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 34-7 (11.8 g, 77% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 77.15; H, 4.27; N, 7.66; Measured C, 77.10; H, 4.26; N, 7.67. Mass spectrometry: Theoretical 730.17; Measured 730.1 (M+).

[0426] Under an argon atmosphere, 34-7 (11.0 g, 15 mmol), pinacol diborate (8.9 g, 35 mmol), potassium acetate (3.4 g, 35 mmol), dioxane (120 mL), and Pd(dppf)Cl2 (0.5 g, 0.7 mmol) were added to a 250 mL round-bottom flask and heated to reflux for 12 hours. After the reaction was complete, the mixture was cooled, the solvent was removed, and the product was hydrolyzed with an aqueous sodium hydroxide solution. The solution was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to give compound 34-8 (7.6 g, 73% yield). Elemental analysis: Theoretical C, 81.04; H, 4.78; N, 8.04; Measured C, 81.00; H, 4.82; N, 8.01. Mass spectrometry: Theoretical 696.27; Measured 696.2 (M+).

[0427] Under an argon atmosphere, 34-8 (7.0 g, 10 mmol), 34-6 (1.6 g, 10 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound H-83 (5.7 g, 78% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical value C, 87.33; H, 4.98; N, 7.69; Measured value C, 87.36; H, 4.98; N, 7.65. Mass spectrometry: Theoretical value 728.29; Measured value 728.2 (M+).

[0428] Example 35

[0429] The reaction is as follows:

[0430]

[0431] Under an argon atmosphere, 35-1 (13.6 g, 40 mmol), 35-2 (14.7 g, 80 mmol), 19.0 g sodium metabisulfite (100 mmol), and N,N-dimethylformamide (140 mL) were added to a 250 mL round-bottom flask. The mixture was heated and stirred at 100 °C for 10 hours. After the reaction solution cooled to room temperature, it was poured into cold water and extracted three times with ethyl acetate (3 × 50 mL). The organic phase was separated, and the product compound (20.5 g, 77% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical value C, 57.59; H, 3.02; N, 8.40; Measured value C, 57.51; H, 3.02; N, 8.19. Mass spectrometry: Theoretical value 665.99; Measured value 665.9 (M+).

[0432] Under an argon atmosphere, 35-3 (20.0 g, 30 mmol), 35-4 (6.4 g, 30 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 35-5 (15.5 g, 73% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 74.68; H, 3.85; N, 7.92; Measured C, 74.72; H, 3.84; N, 7.94. Mass spectrometry: Theoretical 706.14; Measured 706.1 (M+).

[0433] Under an argon atmosphere, 35-5 (14.8 g, 21 mmol), 35-6 (6.3 g, 21 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 35-7 (14.1 g, 76% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 78.82; H, 3.99; N, 6.34; Measured C, 78.80; H, 3.99; N, 6.38. Mass spectrometry: Theoretical 882.20; Measured 882.2 (M+).

[0434] Under an argon atmosphere, 35-7 (13.2 g, 15 mmol), pinacol diborate (8.9 g, 35 mmol), potassium acetate (3.4 g, 35 mmol), dioxane (120 mL), and Pd(dppf)Cl2 (0.5 g, 0.7 mmol) were added to a 250 mL round-bottom flask and heated to reflux for 12 hours. After the reaction was complete, the mixture was cooled, the solvent was removed, and the product was hydrolyzed with an aqueous sodium hydroxide solution. The solution was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain compound 35-8 (10.4 g, 82% yield). Elemental analysis: Theoretical value C, 82.08; H, 4.39; N, 6.60; Measured value C, 82.05; H, 4.42; N, 6.65. Mass spectrometry: Theoretical value 848.30; Measured value 848.3 (M+).

[0435] Under an argon atmosphere, 35-8 (8.5 g, 10 mmol), 35-9 (2.3 g, 10 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound H-87 (7.1 g, 74% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 87.84; H, 4.63; N, 5.85; Measured C, 87.86; H, 4.68; N, 5.82. Mass spectrometry: Theoretical 956.35; Measured 956.3 (M+).

[0436] Example 36

[0437] The reaction is as follows:

[0438]

[0439] Under an argon atmosphere, 36-1 (13.6 g, 40 mmol), 36-2 (14.7 g, 80 mmol), 19.0 g sodium metabisulfite (100 mmol), and N,N-dimethylformamide (140 mL) were added to a 250 mL round-bottom flask. The mixture was heated and stirred at 100 °C for 10 hours. After the reaction solution cooled to room temperature, it was poured into cold water and extracted three times with ethyl acetate (3 × 50 mL). The organic phase was separated, and the product compound 36-3 (20.8 g, 78% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical value C, 57.59; H, 3.02; N, 8.40; Measured value C, 57.52; H, 3.03; N, 831. Mass spectrometry: Theoretical value 665.99; Measured value 665.9 (M+).

[0440] Under an argon atmosphere, 36-3 (20.0 g, 30 mmol), 36-4 (3.8 g, 30 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 36-5 (13.8 g, 74% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 73.31; H, 4.86; N, 9.00; Measured C, 73.30; H, 4.88; N, 9.03. Mass spectrometry: Theoretical 621.16; Measured 621.1 (M+).

[0441] Under an argon atmosphere, 36-5 (13.0 g, 21 mmol), 36-6 (4.2 g, 21 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 36-7 (11.0 g, 75% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 75.64; H, 4.90; N, 8.02; Measured C, 75.61; H, 4.90; N, 8.00. Mass spectrometry: Theoretical 697.19; Measured 397.1 (M+).

[0442] Under an argon atmosphere, 36-7 (7.7 g, 11 mmol), 36-8 (3.3 g, 11 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 36-9 (7.2 g, 75% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 79.63; H, 4.84; N, 6.40; Measured C, 79.68; H, 4.84; N, 6.41. Mass spectrometry: Theoretical 873.25; Measured 873.2 (M+).

[0443] Under an argon atmosphere, 36-9 (6.5 g, 7.5 mmol), pinacol diborate (8.9 g, 35 mmol), potassium acetate (3.4 g, 35 mmol), dioxane (120 mL), and Pd(dppf)Cl2 (0.5 g, 0.7 mmol) were added to a 250 mL round-bottom flask and heated to reflux for 12 hours. After the reaction was complete, the mixture was cooled, the solvent was removed, and the product was hydrolyzed with an aqueous sodium hydroxide solution. The solution was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to give compound 36-10 (5.2 g, 82% yield). Elemental analysis: Theoretical C, 82.95; H, 5.28; N, 6.67; Measured C, 82.96; H, 5.27; N, 6.71. Mass spectrometry: Theoretical 839.35; Measured 839.3 (M+).

[0444] Under an argon atmosphere, 36-10 (4.2 g, 5 mmol), 36-7 (3.5 g, 5 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound H-158 (5.2 g, 73% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 86.6; H, 5.42; N, 7.93; Measured C, 86.6; H, 5.45; N, 7.94. Mass spectrometry: Theoretical 1412.60; Measured 1412.6 (M+).

[0445] Example 37

[0446] The reaction is as follows:

[0447]

[0448] Under an argon atmosphere, 37-1 (13.6 g, 40 mmol), 37-2 (14.7 g, 80 mmol), 19.0 g sodium metabisulfite (100 mmol), and N,N-dimethylformamide (140 mL) were added to a 250 mL round-bottom flask, and the mixture was heated and stirred at 100 °C for 10 hours. After the reaction solution cooled to room temperature, it was poured into cold water and extracted three times with ethyl acetate (3 × 50 mL). The organic phase was separated, and the product compound 37-3 (20.2 g, 76% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical value C, 57.59; H, 3.02; N, 8.40; Measured value C, 57.51; H, 3.08; N, 8.29. Mass spectrometry: Theoretical value 665.99; Measured value 665.9 (M+).

[0449] Under an argon atmosphere, 37-3 (19.3 g, 29 mmol), 37-4 (5.7 g, 29 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 37-5 (15.3 g, 76% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 76.19; H, 4.21; N, 8.08; Measured C, 76.22; H, 4.21; N, 8.00. Mass spectrometry: Theoretical 692.16; Measured 692.1 (M+).

[0450] Under an argon atmosphere, 37-5 (9.0 g, 13 mmol), 37-6 (3.9 g, 13 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 37-7 (8.5 g, 75% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical value C, 80.09; H, 4.29; N, 6.44; Measured value C, 80.13; H, 4.25; N, 6.41. Mass spectrometry: Theoretical value 868.22; Measured value 868.2 (M+).

[0451] Under an argon atmosphere, 37-7 (7.8 g, 9 mmol), pinacol diborate (8.9 g, 35 mmol), potassium acetate (3.4 g, 35 mmol), dioxane (120 mL), and Pd(dppf)Cl2 (0.5 g, 0.7 mmol) were added to a 250 mL round-bottom flask and heated to reflux for 12 hours. After the reaction was complete, the mixture was cooled, the solvent was removed, and hydrolysis was performed with an aqueous sodium hydroxide solution. The product was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain compound 37-8 (6.2 g, 82% yield). Elemental analysis: Theoretical value C, 83.45; H, 4.71; N, 6.71; Measured value C, 83.45; H, 4.74; N, 6.67. Mass spectrometry: Theoretical value 834.32; Measured value 834.3 (M+).

[0452] Under an argon atmosphere, 37-8 (5.0 g, 6 mmol), 37-5 (4.2 g, 6 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound H-98 (6.3 g, 75% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 87.28; H, 4.74; N, 7.98; Measured C, 87.31; H, 4.70; N, 7.95. Mass spectrometry: Theoretical 1402.54; Measured 1402.5 (M+).

[0453] Example 38

[0454] The reaction is as follows:

[0455]

[0456] Under an argon atmosphere, 38-1 (12.4 g, 40 mmol), 38-2 (7.4 g, 40 mmol), 15.2 g sodium metabisulfite (80 mmol), and N,N-dimethylformamide (100 mL) were added to a 250 mL round-bottom flask. The mixture was heated and stirred at 100 °C for 10 hours. After the reaction solution cooled to room temperature, it was poured into cold water and extracted three times with ethyl acetate (3 × 50 mL). The organic phase was separated, and the product compound 38-3 (15.4 g, 81% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical value C, 48.03; H, 2.55; N, 5.90; Measured value C, 48.00; H, 2.54; N, 5.88. Mass spectrometry: Theoretical value 473.92; Measured value 473.9 (M+).

[0457] Under an argon atmosphere, 38-3 (14.7 g, 31 mmol), 38-4 (6.6 g, 31 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 38-5 (11.6 g, 73% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 72.24; H, 3.72; N, 5.44; Measured C, 72.21; H, 3.76; N, 5.42. Mass spectrometry: Theoretical 514.07; Measured 514.0 (M+).

[0458] Under an argon atmosphere, 38-5 (10.3 g, 20 mmol), 38-6 (6.0 g, 20 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 38-7 (10.4 g, 75% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 78.15; H, 3.94; N, 4.05; Measured C, 78.12; H, 3.97; N, 4.06. Mass spectrometry: Theoretical 690.13; Measured 690.1 (M+).

[0459] Under an argon atmosphere, 38-7 (9.7 g, 14 mmol), pinacol diborate (8.9 g, 35 mmol), potassium acetate (3.4 g, 35 mmol), dioxane (120 mL), and Pd(dppf)Cl2 (0.5 g, 0.7 mmol) were added to a 250 mL round-bottom flask and heated to reflux for 12 hours. After the reaction was complete, the mixture was cooled, the solvent was removed, and the product was hydrolyzed with an aqueous sodium hydroxide solution. The solution was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain compound 38-8 (7.3 g, 79% yield). Elemental analysis: Theoretical C, 82.32; H, 4.45; N, 4.27; Measured C, 82.28; H, 4.48; N, 4.27. Mass spectrometry: Theoretical 656.23; Measured 656.2 (M+).

[0460] Under an argon atmosphere, 38-8 (6.6 g, 10 mmol), 38-9 (4.6 g, 10 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound H-99 (5.3 g, 77% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 88.93; H, 4.68; N, 4.07; Measured C, 88.98; H, 4.65; N, 4.07. Mass spectrometry: Theoretical 688.25; Measured 688.2 (M+).

[0461] Example 39

[0462] The reaction is as follows:

[0463]

[0464] Under an argon atmosphere, 39-1 (8.5 g, 40 mmol), 39-2 (14.7 g, 80 mmol), 19.0 g sodium metabisulfite (100 mmol), and N,N-dimethylformamide (140 mL) were added to a 250 mL round-bottom flask. The mixture was heated and stirred at 100 °C for 10 hours. After the reaction solution cooled to room temperature, it was poured into cold water and extracted three times with ethyl acetate (3 × 50 mL). The organic phase was separated, and the product compound 39-3 (16.4 g, 76% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical value C, 70.99; H, 3.91; N, 10.35; Measured value C, 70.94; H, 3.94; N, 10.30. Mass spectrometry: Theoretical value 540.09; Measured value 504.0 (M+).

[0465] Under an argon atmosphere, 39-3 (15.7 g, 29 mmol), 39-4 (8.7 g, 29 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 39-5 (15.8 g, 76% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 76.99; H, 4.07; N, 7.81; Measured C, 76.95; H, 4.02; N, 7.86. Mass spectrometry: Theoretical 716.16; Measured 716.1 (M+).

[0466] Under an argon atmosphere, 39-5 (15.0 g, 21 mmol), pinacol diborate (8.9 g, 35 mmol), potassium acetate (3.4 g, 35 mmol), dioxane (120 mL), and Pd(dppf)Cl2 (0.5 g, 0.7 mmol) were added to a 250 mL round-bottom flask and heated to reflux for 12 hours. After the reaction was complete, the mixture was cooled, the solvent was removed, and the product was hydrolyzed with an aqueous sodium hydroxide solution. The product was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain compound 39-6 (10.5 g, 73% yield). Elemental analysis: Theoretical value C, 80.94; H, 4.58; N, 8.21; Measured value C, 80.92; H, 4.56; N, 8.21. Mass spectrometry: Theoretical value 682.25; Measured value 682.2 (M+).

[0467] Under an argon atmosphere, 39-6 (9.6 g, 14 mmol), 39-7 (3.2 g, 14 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound H-100 (8.5 g, 77% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 88.07; H, 4.84; N, 7.08; Measured C, 88.02; H, 4.87; N, 7.03. Mass spectrometry: Theoretical 790.31; Measured 790.3 (M+).

[0468] Example 40

[0469] The reaction is as follows:

[0470]

[0471] Under an argon atmosphere, 40-1 (12.4 g, 40 mmol), 40-2 (7.4 g, 40 mmol), 15.2 g sodium metabisulfite (80 mmol), and N,N-dimethylformamide (100 mL) were added to a 250 mL round-bottom flask. The mixture was heated and stirred at 100 °C for 10 hours. After the reaction solution cooled to room temperature, it was poured into cold water and extracted three times with ethyl acetate (3 × 50 mL). The organic phase was separated, and the product compound 40-3 (15.2 g, 80% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical value C, 48.03; H, 2.55; N, 5.90; Measured value C, 48.05; H, 2.54; N, 5.82. Mass spectrometry: Theoretical value 473.92; Measured value 473.9 (M+).

[0472] Under an argon atmosphere, 40-3 (14.2 g, 30 mmol), 40-4 (3.7 g, 30 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 40-5 (9.7 g, 76% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 70.60; H, 4.03; N, 6.59; Measured C, 70.66; H, 4.11; N, 6.54. Mass spectrometry: Theoretical 424.06; Measured 424.0 (M+).

[0473] Under an argon atmosphere, 40-5 (8.9 g, 21 mmol), 40-6 (6.3 g, 21 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 40-7 (9.3 g, 74% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 77.87; H, 4.19; N, 4.66; Measured C, 77.84; H, 4.22; N, 4.60. Mass spectrometry: Theoretical 600.12; Measured 600.1 (M+).

[0474] Under an argon atmosphere, 40-7 (8.4 g, 14 mmol), pinacol diborate (8.9 g, 35 mmol), potassium acetate (3.4 g, 35 mmol), dioxane (120 mL), and Pd(dppf)Cl2 (0.5 g, 0.7 mmol) were added to a 250 mL round-bottom flask and heated to reflux for 12 hours. After the reaction was complete, the mixture was cooled, the solvent was removed, and the product was hydrolyzed with an aqueous sodium hydroxide solution. The solution was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain compound 40-8 (6.4 g, 81% yield). Elemental analysis: Theoretical C, 82.69; H, 4.80; N, 4.95; Measured C, 82.64; H, 4.83; N, 4.91. Mass spectrometry: Theoretical 566.22; Measured 566.2 (M+).

[0475] Under an argon atmosphere, 40-8 (5.7 g, 10 mmol), 40-9 (1.6 g, 10 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound H-102 (4.7 g, 79% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 90.27; H, 5.05; N, 4.68; Measured C, 90.31; H, 5.02; N, 4.65. Mass spectrometry: Theoretical 598.24; Measured 598.2 (M+).

[0476] Example 41

[0477] The reaction is as follows:

[0478]

[0479] Under an argon atmosphere, 41-1 (12.4 g, 40 mmol), 41-2 (7.4 g, 40 mmol), 15.2 g sodium metabisulfite (80 mmol), and N,N-dimethylformamide (100 mL) were added to a 250 mL round-bottom flask. The mixture was heated and stirred at 100 °C for 10 hours. After the reaction solution cooled to room temperature, it was poured into cold water and extracted three times with ethyl acetate (3 × 50 mL). The organic phase was separated, and the product compound 41-3 (14.8 g, 78% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical value C, 48.03; H, 2.55; N, 5.90; Measured value C, 48.04; H, 2.52; N, 5.81. Mass spectrometry: Theoretical value 473.92; Measured value 473.9 (M+).

[0480] Under an argon atmosphere, 41-3 (14.2 g, 30 mmol), 41-4 (1.8 g, 30 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 41-5 (8.3 g, 76% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 66.13; H, 4.16; N, 7.71; Measured C, 66.10; H, 4.14; N, 7.71. Mass spectrometry: Theoretical 362.04; Measured 362.0 (M+).

[0481] Under an argon atmosphere, 41-5 (7.2 g, 20 mmol), 41-6 (6.0 g, 20 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 41-7 (7.9 g, 73% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 75.70; H, 4.30; N, 5.19; Measured C, 75.72; H, 4.30; N, 5.14. Mass spectrometry: Theoretical 538.10; Measured 538.1 (M+).

[0482] Under an argon atmosphere, 41-7 (7.0 g, 13 mmol), pinacol diborate (8.9 g, 35 mmol), potassium acetate (3.4 g, 35 mmol), dioxane (120 mL), and Pd(dppf)Cl2 (0.5 g, 0.7 mmol) were added to a 250 mL round-bottom flask and heated to reflux for 12 hours. After the reaction was complete, the mixture was cooled, the solvent was removed, and the product was hydrolyzed with an aqueous sodium hydroxide solution. The solution was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain compound 41-8 (5.4 g, 82% yield). Elemental analysis: Theoretical value C, 80.96; H, 5.00; N, 5.55; Measured value C, 80.90; H, 5.05; N, 5.57. Mass spectrometry: Theoretical value 504.20; Measured value 504.2 (M+).

[0483] Under an argon atmosphere, 41-8 (4.0 g, 8 mmol), 41-9 (1.9 g, 8 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound H-105 (3.8 g, 76% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 88.85; H, 6.64; N, 4.51; Measured C, 88.87; H, 6.60; N, 4.56. Mass spectrometry: Theoretical 621.31; Measured 621.3 (M+).

[0484] Example 42

[0485] The reaction is as follows:

[0486]

[0487] Under an argon atmosphere, 42-1 (13.6 g, 40 mmol), 42-2 (14.7 g, 80 mmol), 19.0 g sodium metabisulfite (100 mmol), and N,N-dimethylformamide (140 mL) were added to a 250 mL round-bottom flask. The mixture was heated and stirred at 100 °C for 10 hours. After the reaction solution cooled to room temperature, it was poured into cold water and extracted three times with ethyl acetate (3 × 50 mL). The organic phase was separated, and the product compound 42-3 (20.5 g, 77% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical value C, 57.59; H, 3.02; N, 8.40; Measured value C, 57.51; H, 3.06; N, 8.29. Mass spectrometry: Theoretical value 665.99; Measured value 665.9 (M+).

[0488] Under an argon atmosphere, 42-3 (20.0 g, 30 mmol), 42-4 (8.3 g, 30 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 42-5 (17.6 g, 76% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical value C, 73.06; H, 3.91; N, 12.69 (test value). Mass spectrometry: Theoretical value 771.17, experimental value 771.10 (M+).

[0489] Under an argon atmosphere, 42-5 (10.8 g, 14 mmol), 42-6 (4.2 g, 14 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 42-7 (9.7 g, 73% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 77.21; H, 4.04; N, 10.33; Measured C, 77.24; H, 4.04; N, 10.35. Mass spectrometry: Theoretical 947.24; Measured 947.2 (M+).

[0490] Under an argon atmosphere, 42-7 (8.5 g, 9 mmol), pinacol diborate (8.9 g, 35 mmol), potassium acetate (3.4 g, 35 mmol), dioxane (120 mL), and Pd(dppf)Cl2 (0.5 g, 0.7 mmol) were added to a 250 mL round-bottom flask and heated to reflux for 12 hours. After the reaction was complete, the mixture was cooled, the solvent was removed, and the product was hydrolyzed with an aqueous sodium hydroxide solution. The product was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain compound 42-8 (6.7 g, 82% yield). Elemental analysis: Theoretical C, 80.17; H, 4.41; N, 10.73; Measured C, 80.20; H, 4.40; N, 10.73. Mass spectrometry: Theoretical 913.33; Measured 913.3 (M+).

[0491] Under an argon atmosphere, 42-8 (5.5 g, 6 mmol), 42-5 (4.6 g, 6 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound H-110 (7.3 g, 78% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical value C, 83.06; H, 4.39; N, 12.56; Measured value C, 83.07; H, 4.30; N, 12.59. Mass spectrometry: Theoretical value 1560.58; Measured value 1560.5 (M+).

[0492] Example 43

[0493] The reaction is as follows:

[0494]

[0495] Under an argon atmosphere, 43-1 (13.6 g, 40 mmol), 43-2 (14.7 g, 80 mmol), 19.0 g sodium metabisulfite (100 mmol), and N,N-dimethylformamide (140 mL) were added to a 250 mL round-bottom flask, and the mixture was heated and stirred at 100 °C for 10 hours. After the reaction solution cooled to room temperature, it was poured into cold water and extracted three times with ethyl acetate (3 × 50 mL). The organic phase was separated, and the product compound 43-3 (20.2 g, 76% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical value C, 57.59; H, 3.02; N, 8.40; Measured value C, 57.50; H, 3.00; N, 8.29. Mass spectrometry: Theoretical value 665.99; Measured value 665.9 (M+).

[0496] Under an argon atmosphere, 43-3 (19.3 g, 29 mmol), 43-4 (3.7 g, 29 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 43-5 (13.7 g, 76% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 73.31; H, 4.86; N, 9.00; Measured C, 73.35; H, 4.82; N, 9.05. Mass spectrometry: Theoretical 621.16; Measured 621.1 (M+).

[0497] Under an argon atmosphere, 43-5 (8.7 g, 14 mmol), 43-6 (4.2 g, 14 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 43-7 (8.3 g, 74% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 78.19; H, 4.79; N, 7.01; Measured C, 78.21; H, 4.79; N, 7.00. Mass spectrometry: Theoretical 797.22; Measured 797.2 (M+).

[0498] Under an argon atmosphere, 43-7 (7.2 g, 9 mmol), pinacol diborate (8.9 g, 35 mmol), potassium acetate (3.4 g, 35 mmol), dioxane (120 mL), and Pd(dppf)Cl2 (0.5 g, 0.7 mmol) were added to a 250 mL round-bottom flask and heated to reflux for 12 hours. After the reaction was complete, the mixture was cooled, the solvent was removed, and the product was hydrolyzed with an aqueous sodium hydroxide solution. The solution was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain compound 43-8 (5.2 g, 75% yield). Elemental analysis: Theoretical C, 81.78; H, 5.28; N, 7.34; Measured C, 81.81; H, 5.29; N, 7.31. Mass spectrometry: Theoretical 763.32; Measured 763.3 (M+).

[0499] Under an argon atmosphere, 43-8 (3.8 g, 5 mmol), 43-5 (3.1 g, 5 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound H-115 (4.85 g, 77% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 85.69; H, 5.43; N, 8.88; Measured C, 85.72; H, 5.46; N, 8.83. Mass spectrometry: Theoretical 1260.54; Measured 1260.5 (M+).

[0500] Example 44

[0501] The reaction is as follows:

[0502]

[0503] Under an argon atmosphere, 44-1 (13.6 g, 40 mmol), 44-2 (14.7 g, 80 mmol), 19.0 g sodium metabisulfite (100 mmol), and N,N-dimethylformamide (140 mL) were added to a 250 mL round-bottom flask, and the mixture was heated and stirred at 100 °C for 10 hours. After the reaction solution cooled to room temperature, it was poured into cold water and extracted three times with ethyl acetate (3 × 50 mL). The organic phase was separated, and the product compound 44-3 (21.0 g, 79% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical value C, 57.59; H, 3.02; N, 8.40; Measured value C, 57.52; H, 3.07; N, 8.29. Mass spectrometry: Theoretical value 665.99; Measured value 665.9 (M+).

[0504] Under an argon atmosphere, 44-3 (20.0 g, 30 mmol), 44-4 (3.7 g, 30 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 44-5 (13.9 g, 75% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 73.91; H, 4.08; N, 9.07; Measured C, 73.92; H, 4.05; N, 9.00. Mass spectrometry: Theoretical 616.13; Measured 616.1 (M+).

[0505] Under an argon atmosphere, 44-5 (8.6 g, 14 mmol), 44-6 (4.2 g, 14 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 44-7 (8.7 g, 78% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 78.68; H, 4.19; N, 7.06; Measured C, 78.72; H, 4.22; N, 7.03. Mass spectrometry: Theoretical 792.19; Measured 792.1 (M+).

[0506] Under an argon atmosphere, 44-7 (7.9 g, 10 mmol), pinacol diborate (8.9 g, 35 mmol), potassium acetate (3.4 g, 35 mmol), dioxane (120 mL), and Pd(dppf)Cl2 (0.5 g, 0.7 mmol) were added to a 250 mL round-bottom flask and heated to reflux for 12 hours. After the reaction was complete, the mixture was cooled, the solvent was removed, and the product was hydrolyzed with an aqueous sodium hydroxide solution. The solution was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain compound 44-8 (6.2 g, 82% yield). Elemental analysis: Theoretical C, 82.32; H, 4.65; N, 7.38; Measured C, 82.30; H, 4.71; N, 7.38. Mass spectrometry: Theoretical 758.29; Measured 758.2 (M+).

[0507] Under an argon atmosphere, 44-8 (5.3 g, 7 mmol), 44-5 (4.3 g, 7 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound H-116 (6.7 g, 76% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 86.37; H, 4.67; N, 8.95; Measured C, 86.33; H, 4.65; N, 8.97. Mass spectrometry: Theoretical 1250.48; Measured 1250.4 (M+).

[0508] Example 45

[0509] The reaction is as follows:

[0510]

[0511] Under an argon atmosphere, 45-1 (13.6 g, 40 mmol), 45-2 (14.7 g, 80 mmol), 19.0 g sodium metabisulfite (100 mmol), and N,N-dimethylformamide (140 mL) were added to a 250 mL round-bottom flask, and the mixture was heated and stirred at 100 °C for 10 hours. After the reaction solution cooled to room temperature, it was poured into cold water and extracted three times with ethyl acetate (3 × 50 mL). The organic phase was separated, and the product compound 45-3 (20.8 g, 78% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical value C, 57.59; H, 3.02; N, 8.40; Measured value C, 57.52; H, 3.01; N, 8.27. Mass spectrometry: Theoretical value 665.99; Measured value 665.9 (M+).

[0512] Under an argon atmosphere, 45-3 (20.0 g, 30 mmol), 45-4 (1.8 g, 30 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 45-5 (12.8 g, 77% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 71.36; H, 4.17; N, 10.09; Measured C, 71.35; H, 4.12; N, 10.11. Mass spectrometry: Theoretical 554.11; Measured 554.1 (M+).

[0513] Under an argon atmosphere, 45-5 (7.8 g, 14 mmol), 45-6 (4.2 g, 14 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 45-7 (7.5 g, 73% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 77.15; H, 4.27; N, 7.66; Measured C, 77.18; H, 4.25; N, 7.66. Mass spectrometry: Theoretical 730.17; Measured 730.1 (M+).

[0514] Under an argon atmosphere, 45-7 (6.6 g, 9 mmol), pinacol diborate (8.9 g, 35 mmol), potassium acetate (3.4 g, 35 mmol), dioxane (120 mL), and Pd(dppf)Cl2 (0.5 g, 0.7 mmol) were added to a 250 mL round-bottom flask and heated to reflux for 12 hours. After the reaction was complete, the mixture was cooled, the solvent was removed, and the product was hydrolyzed with an aqueous sodium hydroxide solution. The product was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain compound 45-8 (5.0 g, 80% yield). Elemental analysis: Theoretical C, 81.04; H, 4.78; N, 8.04; Measured C, 81.04; H, 4.82; N, 8.01. Mass spectrometry: Theoretical 696.27; Measured 696.2 (M+).

[0515] Under an argon atmosphere, 45-8 (4.2 g, 6 mmol), 45-9 (1.0 g, 6 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound H-121 (3.3 g, 74% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 86.74; H, 5.63; N, 7.63; Measured C, 86.74; H, 5.66; N, 7.67. Mass spectrometry: Theoretical 733.33; Measured 733.3 (M+).

[0516] Example 46

[0517] The reaction is as follows:

[0518]

[0519] Under an argon atmosphere, 46-1 (12.4 g, 40 mmol), 46-2 (7.4 g, 40 mmol), 15.2 g sodium metabisulfite (80 mmol), and N,N-dimethylformamide (100 mL) were added to a 250 mL round-bottom flask. The mixture was heated and stirred at 100 °C for 10 hours. After the reaction solution cooled to room temperature, it was poured into cold water and extracted three times with ethyl acetate (3 × 50 mL). The organic phase was separated, and the product compound 46-3 (15.0 g, 79% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical value C, 48.03; H, 2.55; N, 5.90; Measured value C, 48.02; H, 2.53; N, 5.89. Mass spectrometry: Theoretical value 473.92; Measured value 473.9 (M+).

[0520] Under an argon atmosphere, 46-3 (14.2 g, 30 mmol), 46-4 (7.9 g, 30 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 46-5 (12.5 g, 74% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 74.34; H, 3.74; N, 4.95; Measured C, 74.39; H, 3.73; N, 4.95. Mass spectrometry: Theoretical 564.08; Measured 564.0 (M+).

[0521] Under an argon atmosphere, 46-5 (11.3 g, 20 mmol), 46-6 (4.0 g, 20 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 46-7 (9.9 g, 77% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 76.76; H, 3.93; N, 4.37; Measured C, 76.75; H, 3.96; N, 4.30. Mass spectrometry: Theoretical 640.12; Measured 604.1 (M+).

[0522] Under an argon atmosphere, 46-7 (9.0 g, 14 mmol), 46-8 (4.2 g, 14 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 46-9 (8.6 g, 75% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 80.78; H, 4.07; N, 3.43; Measured C, 80.81; H, 4.00; N, 3.41. Mass spectrometry: Theoretical 816.18; Measured 816.1 (M+).

[0523] Under an argon atmosphere, 46-9 (7.3 g, 9 mmol), pinacol diborate (8.9 g, 35 mmol), potassium acetate (3.4 g, 35 mmol), dioxane (120 mL), and Pd(dppf)Cl2 (0.5 g, 0.7 mmol) were added to a 250 mL round-bottom flask and heated to reflux for 12 hours. After the reaction was complete, the mixture was cooled, the solvent was removed, and the product was hydrolyzed with an aqueous sodium hydroxide solution. The solution was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain compound 46-10 (5.5 g, 78% yield). Elemental analysis: Theoretical C, 84.40; H, 4.51; N, 3.58; Measured C, 84.43; H, 4.52; N, 3.58. Mass spectrometry: Theoretical 782.27; Measured 782.2 (M+).

[0524] Under an argon atmosphere, 46-10 (4.7 g, 6 mmol), 46-11 (1.0 g, 6 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound H-124 (3.6 g, 74% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 89.90; H, 4.70; N, 3.44; Measured C, 89.93; H, 4.76; N, 3.41. Mass spectrometry: Theoretical 814.30; Measured 814.3 (M+).

[0525] Example 47

[0526] The reaction is as follows:

[0527]

[0528] Under an argon atmosphere, 47-1 (12.4 g, 40 mmol), 47-2 (7.4 g, 40 mmol), 15.2 g sodium metabisulfite (80 mmol), and N,N-dimethylformamide (100 mL) were added to a 250 mL round-bottom flask. The mixture was heated and stirred at 100 °C for 10 hours. After the reaction solution cooled to room temperature, it was poured into cold water and extracted three times with ethyl acetate (3 × 50 mL). The organic phase was separated, and the product compound 47-3 (15.0 g, 79% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical value C, 48.03; H, 2.55; N, 5.90; Measured value C, 48.01; H, 2.56; N, 5.88. Mass spectrometry: Theoretical value 473.92; Measured value 473.9 (M+).

[0529] Under an argon atmosphere, 47-3 (14.2 g, 30 mmol), 47-4 (1.8 g, 30 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 47-5 (8.0 g, 74% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 66.13; H, 4.16; N, 7.71; Measured C, 66.16; H, 4.14; N, 7.72. Mass spectrometry: Theoretical 362.04; Measured 362.0 (M+).

[0530] Under an argon atmosphere, 47-5 (7.6 g, 21 mmol), 47-6 (6.3 g, 21 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 47-7 (8.6 g, 76% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 75.70; H, 4.30; N, 5.19; Measured C, 75.76; H, 4.33; N, 5.14. Mass spectrometry: Theoretical 538.10; Measured 583.1 (M+).

[0531] Under an argon atmosphere, 47-7 (8.1 g, 15 mmol), pinacol diborate (8.9 g, 35 mmol), potassium acetate (3.4 g, 35 mmol), dioxane (120 mL), and Pd(dppf)Cl2 (0.5 g, 0.7 mmol) were added to a 250 mL round-bottom flask and heated to reflux for 12 hours. After the reaction was complete, the mixture was cooled, the solvent was removed, and the product was hydrolyzed with an aqueous sodium hydroxide solution. The product was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain compound 47-8 (5.7 g, 75% yield). Elemental analysis: Theoretical C, 80.96; H, 5.00; N, 5.55; Measured C, 80.92; H, 5.06; N, 5.51. Mass spectrometry: Theoretical 504.20; Measured 504.2 (M+).

[0532] Under an argon atmosphere, 47-8 (5.0 g, 10 mmol), 47-9 (1.6 g, 10 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound H-125 (4.2 g, 78% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical value C, 89.52; H, 5.26; N, 5.22; Measured value C, 89.53; H, 5.24; N, 5.21. Mass spectrometry: Theoretical value 536.23; Measured value 536.2 (M+).

[0533] Example 48

[0534] The reaction is as follows:

[0535]

[0536] Under an argon atmosphere, 48-1 (12.4 g, 40 mmol), 48-2 (7.4 g, 40 mmol), 15.2 g sodium metabisulfite (80 mmol), and N,N-dimethylformamide (100 mL) were added to a 250 mL round-bottom flask. The mixture was heated and stirred at 100 °C for 10 hours. After the reaction solution cooled to room temperature, it was poured into cold water and extracted three times with ethyl acetate (3 × 50 mL). The organic phase was separated, and the product compound 48-3 (14.6 g, 77% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical value C, 48.03; H, 2.55; N, 5.90; Measured value C, 48.02; H, 2.52; N, 5.89. Mass spectrometry: Theoretical value 473.92; Measured value 473.9 (M+).

[0537] Under an argon atmosphere, 48-3 (14.2 g, 30 mmol), 48-4 (5.9 g, 30 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 48-5 (11.1 g, 74% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical value C, 74.26; H, 4.22; N, 5.59; Measured value C, 74.23; H, 4.24; N, 5.56. Mass spectrometry: Theoretical value 500.09; Measured value 500.0 (M+).

[0538] Under an argon atmosphere, 48-5 (10.0 g, 20 mmol), 48-6 (6.0 g, 20 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 48-7 (10.7 g, 79% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 79.76; H, 4.31; N, 4.13; Measured C, 79.75; H, 4.30; N, 4.18. Mass spectrometry: Theoretical 676.15; Measured 676.1 (M+).

[0539] Under an argon atmosphere, 48-7 (9.5 g, 14 mmol), pinacol diborate (8.9 g, 35 mmol), potassium acetate (3.4 g, 35 mmol), dioxane (120 mL), and Pd(dppf)Cl2 (0.5 g, 0.7 mmol) were added to a 250 mL round-bottom flask and heated to reflux for 12 hours. After the reaction was complete, the mixture was cooled, the solvent was removed, and the product was hydrolyzed with an aqueous sodium hydroxide solution. The solution was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain compound 48-8 (6.6 g, 73% yield). Elemental analysis: Theoretical value C, 84.12; H, 4.86; N, 4.36; Measured value C, 84.12; H, 4.87; N, 4.35. Mass spectrometry: Theoretical value 642.25; Measured value 642.2 (M+).

[0540] Under an argon atmosphere, 48-8 (5.8 g, 9 mmol), 48-9 (1.4 g, 9 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound H-126 (4.6 g, 75% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical value C, 90.77; H, 5.08; N, 4.15; Measured value C, 90.74; H, 5.03; N, 4.14. Mass spectrometry: Theoretical value 674.27; Measured value 674.2 (M+).

[0541] Example 49

[0542] The reaction is as follows:

[0543]

[0544] Under an argon atmosphere, (13.6 g, 40 mmol), (14.7 g, 80 mmol), 19.0 g sodium metabisulfite (100 mmol), and N,N-dimethylformamide (140 mL) were added to a 250 mL round-bottom flask. The mixture was heated and stirred at 100 °C for 10 hours. After the reaction solution cooled to room temperature, it was poured into cold water and extracted three times with ethyl acetate (3 × 50 mL). The organic phase was separated, and the product compound (20.8 g, 78% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical value C, 57.59; H, 3.02; N, 8.40; Measured value C, 57.52; H, 3.05; N, 8.20. Mass spectrometry: Theoretical value 665.99; Measured value 665.9 (M+).

[0545] Under an argon atmosphere, 49-3 (20.0 g, 30 mmol), 49-4 (3.7 g, 30 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 49-5 (14.0 g, 76% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 73.91; H, 4.08; N, 9.07; Measured C, 73.96; H, 4.06; N, 9.00. Mass spectrometry: Theoretical 616.13; Measured 616.1 (M+).

[0546] Under an argon atmosphere, 49-5 (12.9 g, 21 mmol), 49-6 (6.3 g, 21 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 49-7 (12.3 g, 74% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 78.68; H, 4.19; N, 7.06; Measured C, 78.65; H, 4.13; N, 7.05. Mass spectrometry: Theoretical 792.19; Measured 792.1 (M+).

[0547] Under an argon atmosphere, 49-7 (11.1 g, 14 mmol), pinacol diborate (8.9 g, 35 mmol), potassium acetate (3.4 g, 35 mmol), dioxane (120 mL), and Pd(dppf)Cl2 (0.5 g, 0.7 mmol) were added to a 250 mL round-bottom flask and heated to reflux for 12 hours. After the reaction was complete, the mixture was cooled, the solvent was removed, and the product was hydrolyzed with an aqueous sodium hydroxide solution. The product was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain compound 49-8 (8.5 g, 80% yield). Elemental analysis: Theoretical C, 82.32; H, 4.65; N, 7.38; Measured C, 82.30; H, 4.69; N, 7.38. Mass spectrometry: Theoretical 758.29; Measured 758.2 (M+).

[0548] Under an argon atmosphere, 49-8 (7.6 g, 10 mmol), 49-9 (1.6 g, 10 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound H-127 (5.8 g, 73% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical value C, 87.52; H, 5.44; N, 7.04; Measured value C, 87.50; H, 5.46; N, 7.08. Mass spectrometry: Theoretical value 795.34; Measured value 795.3 (M+).

[0549] Example 50

[0550] The reaction is as follows:

[0551]

[0552] Under an argon atmosphere, 50-1 (13.6 g, 40 mmol), 50-2 (14.7 g, 80 mmol), 19.0 g sodium metabisulfite (100 mmol), and N,N-dimethylformamide (140 mL) were added to a 250 mL round-bottom flask, and the mixture was heated and stirred at 100 °C for 10 hours. After the reaction solution cooled to room temperature, it was poured into cold water and extracted three times with ethyl acetate (3 × 50 mL). The organic phase was separated, and the product compound 50-3 (20.3 g, 76% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical value C, 57.59; H, 3.02; N, 8.40; Measured value C, 57.50; H, 3.06; N, 8.29. Mass spectrometry: Theoretical value 665.99; Measured value 665.9 (M+).

[0553] Under an argon atmosphere, 50-3 (19.4 g, 29 mmol), 50-4 (3.5 g, 29 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 50-5 (13.9 g, 78% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 73.91; H, 4.08; N, 9.07; Measured C, 73.98; H, 4.00; N, 9.05. Mass spectrometry: Theoretical 616.13; Measured 616.1 (M+).

[0554] Under an argon atmosphere, 50-5 (12.3 g, 20 mmol), 50-6 (6.0 g, 20 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 50-7 (11.7 g, 74% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 78.68; H, 4.19; N, 7.06; Measured C, 78.72; H, 4.25; N, 7.00. Mass spectrometry: Theoretical 792.19; Measured 792.1 (M+).

[0555] Under an argon atmosphere, 50-7 (11.1 g, 14 mmol), pinacol diborate (8.9 g, 35 mmol), potassium acetate (3.4 g, 35 mmol), dioxane (120 mL), and Pd(dppf)Cl2 (0.5 g, 0.7 mmol) were added to a 250 mL round-bottom flask and heated to reflux for 12 hours. After the reaction was complete, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The product was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain compound 50-8 (8.4 g, 79% yield). Elemental analysis: Theoretical value C, 82.32; H, 4.65; N, 7.38; Measured value C, 82.32; H, 4.63; N, 7.41. Mass spectrometry: Theoretical value 758.29; Measured value 758.2 (M+).

[0556] Under an argon atmosphere, 50-8 (7.6 g, 10 mmol), 50-9 (2.3 g, 10 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound H-128 (6.5 g, 75% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 88.66; H, 4.88; N, 6.46; Measured C, 88.69; H, 4.92; N, 6.42. Mass spectrometry: Theoretical 866.34; Measured 866.3 (M+).

[0557] Example 51

[0558] The reaction is as follows:

[0559]

[0560] Under an argon atmosphere, 51-1 (12.4 g, 40 mmol), 51-2 (7.4 g, 40 mmol), 15.2 g sodium metabisulfite (80 mmol), and N,N-dimethylformamide (100 mL) were added to a 250 mL round-bottom flask. The mixture was heated and stirred at 100 °C for 10 hours. After the reaction solution cooled to room temperature, it was poured into cold water and extracted three times with ethyl acetate (3 × 50 mL). The organic phase was separated, and the product compound 51-3 (14.8 g, 78% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical value C, 48.03; H, 2.55; N, 5.90; Measured value C, 48.00; H, 2.56; N, 5.92. Mass spectrometry: Theoretical value 473.92; Measured value 473.9 (M+).

[0561] Under an argon atmosphere, 51-3 (14.2 g, 30 mmol), 51-4 (1.8 g, 30 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 51-5 (8.1 g, 75% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 66.13; H, 4.16; N, 7.71; Measured C, 66.12; H, 4.17; N, 7.76. Mass spectrometry: Theoretical 362.04; Measured 362.0 (M+).

[0562] Under an argon atmosphere, 51-5 (7.6 g, 21 mmol), 51-6 (6.3 g, 21 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 51-7 (8.4 g, 74% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 75.70; H, 4.30; N, 5.19; Measured C, 75.72; H, 4.33; N, 5.17. Mass spectrometry: Theoretical 538.10; Measured 538.1 (M+).

[0563] Under an argon atmosphere, 51-7 (7.5 g, 14 mmol), pinacol diborate (8.9 g, 35 mmol), potassium acetate (3.4 g, 35 mmol), dioxane (120 mL), and Pd(dppf)Cl2 (0.5 g, 0.7 mmol) were added to a 250 mL round-bottom flask and heated to reflux for 12 hours. After the reaction was complete, the mixture was cooled, the solvent was removed, and the product was hydrolyzed with an aqueous sodium hydroxide solution. The product was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain compound 51-8 (5.8 g, 82% yield). Elemental analysis: Theoretical C, 80.96; H, 8.00; N, 5.55; Measured C, 80.92; H, 8.00; N, 5.56. Mass spectrometry: Theoretical 504.20; Measured 504.2 (M+).

[0564] Under an argon atmosphere, 51-8 (5.0 g, 10 mmol), 51-9 (2.1 g, 10 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound H-135 (4.4 g, 75% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical value C, 90.07; H, 5.15; N, 4.77; Measured value C, 90.01; H, 5.12; N, 4.79. Mass spectrometry: Theoretical value 586.74; Measured value 586.7 (M+).

[0565] Example 52

[0566] The reaction is as follows:

[0567]

[0568] Under an argon atmosphere, 52-1 (12.4 g, 40 mmol), 52-2 (7.4 g, 40 mmol), 15.2 g sodium metabisulfite (80 mmol), and N,N-dimethylformamide (100 mL) were added to a 250 mL round-bottom flask. The mixture was heated and stirred at 100 °C for 10 hours. After the reaction solution cooled to room temperature, it was poured into cold water and extracted three times with ethyl acetate (3 × 50 mL). The organic phase was separated, and the product compound 52-3 (15.2 g, 80% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical value C, 48.03; H, 2.55; N, 5.90; Measured value C, 48.01; H, 2.52; N, 5.86. Mass spectrometry: Theoretical value 473.92; Measured value 473.9 (M+).

[0569] Under an argon atmosphere, 52-3 (14.2 g, 30 mmol), 52-4 (6.4 g, 30 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 52-5 (11.7 g, 76% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 72.24; H, 3.72; N, 5.44; Measured C, 72.22; H, 3.75; N, 5.49. Mass spectrometry: Theoretical 514.07; Measured 514.0 (M+).

[0570] Under an argon atmosphere, 52-5 (10.8 g, 21 mmol), 52-6 (4.2 g, 21 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 52-7 (9.2 g, 74% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 75.13; H, 3.92; N, 4.74; Measured C, 75.10; H, 3.94; N, 4.75. Mass spectrometry: Theoretical 590.10; Measured 590.1 (M+).

[0571] Under an argon atmosphere, 52-8 (13.6 g, 40 mmol), 52-2 (14.7 g, 80 mmol), 19.0 g sodium metabisulfite (100 mmol), and N,N-dimethylformamide (140 mL) were added to a 250 mL round-bottom flask, and the mixture was heated and stirred at 100 °C for 10 hours. After the reaction solution cooled to room temperature, it was poured into cold water and extracted three times with ethyl acetate (3 × 50 mL). The organic phase was separated, and the product compound 52-9 (20.5 g, 77% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical value C, 57.59; H, 3.02; N, 8.40; Measured value C, 57.54; H, 3.03; N, 8.21. Mass spectrometry: Theoretical value 665.99; Measured value 665.9 (M+).

[0572] Under an argon atmosphere, 52-9 (20.0 g, 30 mmol), 52-4 (6.4 g, 30 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 52-10 (16.1 g, 76% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 74.68; H, 3.85; N, 7.92; Measured C, 74.67; H, 3.85; N, 7.90. Mass spectrometry: Theoretical 706.14; Measured 706.1 (M+).

[0573] Under an argon atmosphere, 52-10 (14.8 g, 21 mmol), 52-6 (4.2 g, 21 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 52-11 (12.2 g, 74% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 76.63; H, 3.99; N, 7.15; Measured C, 76.65; H, 3.93; N, 7.16. Mass spectrometry: Theoretical 782.17; Measured 782.1 (M+).

[0574] Under an argon atmosphere, 52-11 (11.0 g, 14 mmol), 52-12 (4.2 g, 14 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 52-13 (10.3 g, 77% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical value C, 80.08; H, 4.10; N, 5.84; Measured value C, 80.12; H, 4.06; N, 5.82. Mass spectrometry: Theoretical value 958.23; Measured value 958.2 (M+).

[0575] Under an argon atmosphere, 52-13 (9.6 g, 10 mmol), pinacol diborate (8.9 g, 35 mmol), potassium acetate (3.4 g, 35 mmol), dioxane (120 mL), and Pd(dppf)Cl2 (0.5 g, 0.7 mmol) were added to a 250 mL round-bottom flask and heated to reflux for 12 hours. After the reaction was complete, the mixture was cooled, the solvent was removed, and the product was hydrolyzed with an aqueous sodium hydroxide solution. The product was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain compound 52-14 (7.6 g, 82% yield). Elemental analysis: Theoretical C, 83.12; H, 4.47; N, 6.06; Measured C, 83.10; H, 4.43; N, 6.10. Mass spectrometry: Theoretical 924.33; Measured 924.3 (M+).

[0576] Under an argon atmosphere, 52-14 (6.5 g, 7 mmol), 52-7 (4.1 g, 7 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound H-136 (7.0 g, 72% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 87.17; H, 4.49; N, 6.04; Measured C, 87.21; H, 4.53; N, 6.04. Mass spectrometry: Theoretical 1390.49; Measured 1390.4 (M+).

[0577] Example 53

[0578] The reaction is as follows:

[0579]

[0580] Under an argon atmosphere, 12.4 g (40 mmol) of compound 53-1, 7.4 g (40 mmol) of compound 53-2, 15.2 g (80 mmol) of sodium metabisulfite, and 100 mL of N,N-dimethylformamide were added to a 250 mL round-bottom flask. The mixture was heated and stirred at 100 °C for 10 hours. After the reaction solution cooled to room temperature, it was poured into cold water and extracted three times with ethyl acetate (3 × 50 mL). The organic phase was separated, and the product compound 53-3 (15.2 g, 80% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical value C, 48.03; H, 2.55; N, 5.90; Measured value C, 48.03; H, 2.50; N, 5.88. Mass spectrometry: Theoretical value 473.92; Measured value 473.9 (M+).

[0581] Under an argon atmosphere, 53-3 (14.7 g, 31 mmol), 53-4 (8.1 g, 31 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 53-5 (13.1 g, 75% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 74.34; H, 3.74; N, 4.95; Measured C, 74.36; H, 3.71; N, 4.96. Mass spectrometry: Theoretical 564.08; Measured 564.0 (M+).

[0582] Under an argon atmosphere, 53-5 (11.3 g, 20 mmol), 53-6 (4.0 g, 20 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 53-7 (9.3 g, 73% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 76.76; H, 3.93; N, 4.37; Measured C, 76.75; H, 3.92; N, 4.30. Mass spectrometry: Theoretical 640.12; Measured 640.1 (M+).

[0583] Under an argon atmosphere, 53-8 (13.6 g, 40 mmol), 53-2 (14.7 g, 80 mmol), 19.0 g sodium metabisulfite (100 mmol), and N,N-dimethylformamide (140 mL) were added to a 250 mL round-bottom flask, and the mixture was heated and stirred at 100 °C for 10 hours. After the reaction solution cooled to room temperature, it was poured into cold water and extracted three times with ethyl acetate (3 × 50 mL). The organic phase was separated, and the product compound 53-9 (20.8 g, 78% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical value C, 57.59; H, 3.02; N, 8.40; Measured value C, 57.50; H, 3.03; N, 8.25. Mass spectrometry: Theoretical value 665.99; Measured value 665.9 (M+).

[0584] Under an argon atmosphere, 53-9 (20.0 g, 30 mmol), 53-4 (7.9 g, 30 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 53-10 (17.2 g, 76% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 76.09; H, 3.86; N, 7.39; Measured C, 76.11; H, 3.84; N, 7.42. Mass spectrometry: Theoretical 756.15; Measured 756.1 (M+).

[0585] Under an argon atmosphere, 53-10 (15.9 g, 21 mmol), 53-6 (4.2 g, 21 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 53-11 (13.5 g, 77% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 77.79; H, 3.99; N, 6.72; Measured C, 77.82; H, 4.05; N, 6.70. Mass spectrometry: Theoretical 832.18; Measured 832.1 (M+).

[0586] Under an argon atmosphere, 53-11 (12.5 g, 15 mmol), 53-12 (4.5 g, 15 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 53-13 (11.0 g, 73% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical value C, 80.87; H, 4.09; N, 5.55; Measured value C, 80.91; H, 4.12; N, 5.52. Mass spectrometry: Theoretical value 1008.25; Measured value 1008.2 (M+).

[0587] Under an argon atmosphere, 53-13 (10.1 g, 10 mmol), pinacol diborate (8.9 g, 35 mmol), potassium acetate (3.4 g, 35 mmol), dioxane (120 mL), and Pd(dppf)Cl2 (0.5 g, 0.7 mmol) were added to a 250 mL round-bottom flask and heated to reflux for 12 hours. After the reaction was complete, the mixture was cooled, the solvent was removed, and hydrolysis was performed with an aqueous sodium hydroxide solution. The product was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain compound 53-14 (7.6 g, 78% yield). Elemental analysis: Theoretical value C, 83.78; H, 4.45; N, 5.75; Measured value C, 83.81; H, 4.45; N, 5.79. Mass spectrometry: Theoretical value 974.34; Measured value 974.3 (M+).

[0588] Under an argon atmosphere, 53-14 (6.8 g, 7 mmol), 53-7 (4.5 g, 7 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound H-137 (7.3 g, 70% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 87.67; H, 4.46; N, 5.63; Measured C, 87.70; H, 4.51; N, 5.60. Mass spectrometry: Theoretical 1490.52; Measured 1490.5 (M+).

[0589] Example 54

[0590] The reaction is as follows:

[0591]

[0592] Under an argon atmosphere, 54-1 (12.4 g, 40 mmol), 54-2 (7.4 g, 40 mmol), 15.2 g sodium metabisulfite (80 mmol), and N,N-dimethylformamide (100 mL) were added to a 250 mL round-bottom flask. The mixture was heated and stirred at 100 °C for 10 hours. After the reaction solution cooled to room temperature, it was poured into cold water and extracted three times with ethyl acetate (3 × 50 mL). The organic phase was separated, and the product compound 54-3 (14.8 g, 78% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical value C, 48.03; H, 2.55; N, 5.90; Measured value C, 48.00; H, 2.51; N, 5.86. Mass spectrometry: Theoretical value 473.92; Measured value 473.9 (M+).

[0593] Under an argon atmosphere, 54-3 (14.2 g, 30 mmol), 54-4 (8.3 g, 30 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 54-5 (12.9 g, 74% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 70.35; H, 3.82; N, 12.06; Measured C, 70.41; H, 3.80; N, 12.08. Mass spectrometry: Theoretical 579.11; Measured 579.1 (M+).

[0594] Under an argon atmosphere, 54-5 (11.6 g, 20 mmol), 54-6 (4.0 g, 20 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 54-7 (9.8 g, 75% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 73.17; H, 3.99; N, 10.67; Measured C, 73.21; H, 3.92; N, 10.66. Mass spectrometry: Theoretical 655.14; Measured 655.1 (M+).

[0595] Under an argon atmosphere, 13.6 g (40 mmol) of 54-8, 14.7 g (80 mmol) of 54-2, 19.0 g of sodium metabisulfite (100 mmol) and 140 mL of N,N-dimethylformamide were added to a 250 mL round-bottom flask. The mixture was heated and stirred at 100 °C for 10 hours. After the reaction solution cooled to room temperature, it was poured into cold water and extracted three times with ethyl acetate (3 × 50 mL). The organic phase was separated, and the product compound 54-9 (20.5 g, 77% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical value C, 57.59; H, 3.02; N, 8.40; Measured value C, 57.51; H, 3.06; N, 8.27. Mass spectrometry: Theoretical value 665.99; Measured value 665.9 (M+).

[0596] Under an argon atmosphere, 54-9 (20.0 g, 30 mmol), 54-4 (8.3 g, 30 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 54-10 (17.4 g, 75% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 73.06; H, 3.91; N, 12.69; Measured C, 73.11; H, 3.90; N, 12.65. Mass spectrometry: Theoretical 771.17; Measured 771.1 (M+).

[0597] Under an argon atmosphere, 54-10 (16.2 g, 21 mmol), 54-6 (4.2 g, 21 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 54-11 (13.3 g, 75% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 75.00; H, 4.04; N, 11.55; Measured C, 75.05; H, 4.02; N, 11.54. Mass spectrometry: Theoretical 847.21; Measured 847.2 (M+).

[0598] Under an argon atmosphere, 54-11 (11.9 g, 14 mmol), 54-12 (4.2 g, 14 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 54-13 (10.3 g, 72% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 78.51; H, 4.13; N, 9.57; Measured C, 78.56; H, 4.10; N, 9.61. Mass spectrometry: Theoretical 1023.27; Measured 1023.2 (M+).

[0599] Under an argon atmosphere, 54-13 (9.2 g, 9 mmol), pinacol diborate (8.9 g, 35 mmol), potassium acetate (3.4 g, 35 mmol), dioxane (120 mL), and Pd(dppf)Cl2 (0.5 g, 0.7 mmol) were added to a 250 mL round-bottom flask and heated to reflux for 12 hours. After the reaction was complete, the mixture was cooled, the solvent was removed, and the product was hydrolyzed with an aqueous sodium hydroxide solution. The solution was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain compound 54-14 (7.0 g, 79% yield). Elemental analysis: Theoretical value C, 81.29; H, 4.48; N, 9.90; Measured value C, 81.31; H, 4.50; N, 9.97. Mass spectrometry: Theoretical value 989.39; Measured value 989.3 (M+).

[0600] Under an argon atmosphere, 54-14 (5.9 g, 6 mmol), 54-7 (3.9 g, 6 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound H-138 (6.4 g, 70% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 84.45; H, 4.50; N, 11.05; Measured C, 84.51; H, 4.52; N, 11.06. Mass spectrometry: Theoretical 1520.57; Measured 1520.5 (M+).

[0601] Example 55

[0602] The reaction is as follows:

[0603]

[0604] Under an argon atmosphere, 55-1 (13.6 g, 40 mmol), 55-2 (14.7 g, 80 mmol), 19.0 g sodium metabisulfite (100 mmol), and N,N-dimethylformamide (140 mL) were added to a 250 mL round-bottom flask. The mixture was heated and stirred at 100 °C for 10 hours. After the reaction solution cooled to room temperature, it was poured into cold water and extracted three times with ethyl acetate (3 × 50 mL). The organic phase was separated, and the product compound 55-3 (20.8 g, 78% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical value C, 57.59; H, 3.02; N, 8.40; Measured value C, 57.50; H, 3.09; N, 8.29. Mass spectrometry: Theoretical value 665.99; Measured value 665.9 (M+).

[0605] Under an argon atmosphere, 55-3 (20.0 g, 30 mmol), 55-4 (5.9 g, 30 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 55-5 (15.8 g, 76% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 76.19; H, 4.21; N, 8.08; Measured C, 76.22; H, 4.21; N, 8.06. Mass spectrometry: Theoretical 692.16; Measured 692.1 (M+).

[0606] Under an argon atmosphere, 55-5 (15.2 g, 22 mmol), 55-6 (4.4 g, 22 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 55-7 (13.0 g, 77% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 78.02; H, 4.32; N, 7.28; Measured C, 78.04; H, 4.29; N, 7.25. Mass spectrometry: Theoretical 768.19; Measured 768.1 (M+).

[0607] Under an argon atmosphere, 55-7 (8.5 g, 11 mmol), 55-8 (3.3 g, 11 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 55-9 (8.1 g, 78% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 81.26; H, 4.37; N, 5.92; Measured C, 81.21; H, 4.37; N, 5.90. Mass spectrometry: Theoretical 944.25; Measured 944.2 (M+).

[0608] Under an argon atmosphere, 55-9 (7.1 g, 7.5 mmol), pinacol diborate (8.9 g, 35 mmol), potassium acetate (3.4 g, 35 mmol), dioxane (120 mL), and Pd(dppf)Cl2 (0.5 g, 0.7 mmol) were added to a 250 mL round-bottom flask and heated to reflux for 12 hours. After the reaction was complete, the mixture was cooled, the solvent was removed, and the product was hydrolyzed with an aqueous sodium hydroxide solution. The product was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain compound 55-10 (5.7 g, 83% yield). Elemental analysis: Theoretical value C, 84.39; H, 4.76; N, 6.15; Measured value C, 84.41; H, 4.72; N, 6.15. Mass spectrometry: Theoretical value 910.35; Measured value 910.3 (M+).

[0609] Under an argon atmosphere, 55-10 (5.0 g, 5.5 mmol), 55-7 (4.2 g, 5.5 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound H-139 (6.3 g, 74% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical value C, 88.00; H, 4.79; N, 7.20; Measured value C, 88.01; H, 4.79; N, 7.24. Mass spectrometry: Theoretical value 1554.60; Measured value 1554.6 (M+).

[0610] Example 56

[0611] The reaction is as follows:

[0612]

[0613] Under an argon atmosphere, 56-1 (13.6 g, 40 mmol), 56-2 (14.7 g, 80 mmol), 19.0 g sodium metabisulfite (100 mmol), and N,N-dimethylformamide (140 mL) were added to a 250 mL round-bottom flask. The mixture was heated and stirred at 100 °C for 10 hours. After the reaction solution cooled to room temperature, it was poured into cold water and extracted three times with ethyl acetate (3 × 50 mL). The organic phase was separated, and the product compound 56-3 (20.5 g, 77% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical value C, 57.59; H, 3.02; N, 8.40; Measured value C, 57.51; H, 3.04; N, 8.29. Mass spectrometry: Theoretical value 665.99; Measured value 665.9 (M+).

[0614] Under an argon atmosphere, 56-3 (20.0 g, 30 mmol), 56-4 (6.4 g, 30 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 56-5 (16.3 g, 77% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 74.68; H, 3.85; N, 7.92; Measured C, 74.71; H, 3.80; N, 7.96. Mass spectrometry: Theoretical 706.14; Measured 706.1 (M+).

[0615] Under an argon atmosphere, 56-5 (15.5 g, 22 mmol), 56-6 (4.4 g, 22 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 56-7 (13.1 g, 76% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 76.63; H, 3.99; N, 7.15; Measured C, 76.60; H, 3.94; N, 7.16. Mass spectrometry: Theoretical 782.17; Measured 782.1 (M+).

[0616] Under an argon atmosphere, 56-7 (8.6 g, 11 mmol), 56-8 (3.3 g, 11 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 56-9 (8.0 g, 74% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 80.08; H, 4.10; N, 5.84; Measured C, 80.04; H, 4.13; N, 5.80. Mass spectrometry: Theoretical 958.23; Measured 958.2 (M+).

[0617] Under an argon atmosphere, 56-9 (7.2 g, 7.5 mmol), pinacol diborate (8.9 g, 35 mmol), potassium acetate (3.4 g, 35 mmol), dioxane (120 mL), and Pd(dppf)Cl2 (0.5 g, 0.7 mmol) were added to a 250 mL round-bottom flask and heated to reflux for 12 hours. After the reaction was complete, the mixture was cooled, the solvent was removed, and the product was hydrolyzed with an aqueous sodium hydroxide solution. The product was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain compound 56-10 (5.6 g, 81% yield). Elemental analysis: Theoretical C, 83.12; H, 4.47; N, 6.06; Measured C, 83.08; H, 4.43; N, 6.06. Mass spectrometry: Theoretical 924.33; Measured 924.3 (M+).

[0618] Under an argon atmosphere, 56-10 (4.6 g, 5 mmol), 56-7 (3.9 g, 5 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound H-140 (5.8 g, 73% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 86.45; H, 4.45; N, 7.07; Measured values: 86.50; H, 4.45; N, 7.05. Mass spectrometry: Theoretical 1582.56; Measured 11582.5 (M+).

[0619] Example 57

[0620] The reaction is as follows:

[0621]

[0622] Under an argon atmosphere, 57-1 (13.6 g, 40 mmol), 57-2 (14.7 g, 80 mmol), 19.0 g sodium metabisulfite (100 mmol), and N,N-dimethylformamide (140 mL) were added to a 250 mL round-bottom flask, and the mixture was heated and stirred at 100 °C for 10 hours. After the reaction solution cooled to room temperature, it was poured into cold water and extracted three times with ethyl acetate (3 × 50 mL). The organic phase was separated, and the product compound 57-3 (20.2 g, 76% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical value C, 57.59; H, 3.02; N, 8.40; Measured value C, 57.50; H, 3.05; N, 8.26. Mass spectrometry: Theoretical value 665.99; Measured value 665.9 (M+).

[0623] Under an argon atmosphere, 57-3 (19.3 g, 29 mmol), 57-4 (7.9 g, 29 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 57-5 (13.9 g, 76% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 78.02; H, 4.32; N, 7.28; Measured C, 78.08; H, 4.32; N, 7.29. Mass spectrometry: Theoretical 768.19; Measured 768.1 (M+).

[0624] Under an argon atmosphere, 57-5 (16.1 g, 21 mmol), 57-6 (4.2 g, 21 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 57-7 (13.8 g, 78% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 79.52; H, 4.41; N, 6.62; Measured C, 79.50; H, 4.46; N, 6.62. Mass spectrometry: Theoretical 844.22; Measured 844.2 (M+).

[0625] Under an argon atmosphere, 57-7 (9.3 g, 11 mmol), 57-8 (3.3 g, 11 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 57-9 (8.4 g, 75% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 82.26; H, 4.44; N, 5.48; Measured C, 82.31; H, 4.41; N, 5.45. Mass spectrometry: Theoretical 1020.28; Measured 1020.2 (M+).

[0626] Under an argon atmosphere, 57-9 (7.7 g, 7.5 mmol), pinacol diborate (8.9 g, 35 mmol), potassium acetate (3.4 g, 35 mmol), dioxane (120 mL), and Pd(dppf)Cl2 (0.5 g, 0.7 mmol) were added to a 250 mL round-bottom flask and heated to reflux for 12 hours. After the reaction was complete, the mixture was cooled, the solvent was removed, and the product was hydrolyzed with an aqueous sodium hydroxide solution. The solution was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain compound 57-10 (6.1 g, 82% yield). Elemental analysis: Theoretical C, 85.19; H, 4.80; N, 5.68; Measured C, 85.26; H, 4.80; N, 5.71. Mass spectrometry: Theoretical 986.38; Measured 986.3 (M+).

[0627] Under an argon atmosphere, 57-10 (4.9 g, 5 mmol), 57-7 (4.2 g, 5 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound H-141 (6.7 g, 78% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 88.60; H, 4.84; N, 6.56; Measured C, 88.62; H, 4.81; N, 6.61. Mass spectrometry: Theoretical 1706.67; Measured 1706.6 (M+).

[0628] Example 58

[0629] The reaction is as follows:

[0630]

[0631] Under an argon atmosphere, 13.6 g (40 mmol) of 58-1, 14.7 g (80 mmol) of 58-2, 19.0 g of sodium metabisulfite (100 mmol) and 140 mL of N,N-dimethylformamide were added to a 250 mL round-bottom flask. The mixture was heated and stirred at 100 °C for 10 hours. After the reaction solution cooled to room temperature, it was poured into cold water and extracted three times with ethyl acetate (3 × 50 mL). The organic phase was separated, and the product compound 58-3 (21.0 g, 79% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical value C, 57.59; H, 3.02; N, 8.40; Measured value C, 57.56; H, 3.01; N, 8.27. Mass spectrometry: Theoretical value 665.99; Measured value 665.9 (M+).

[0632] Under an argon atmosphere, 58-3 (20.0 g, 30 mmol), 58-4 (7.9 g, 30 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 58-5 (17.2 g, 76% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 76.09; H, 3.86; N, 7.39; Measured C, 76.11; H, 3.83; N, 7.37. Mass spectrometry: Theoretical 756.15; Measured 756.1 (M+).

[0633] Under an argon atmosphere, 58-5 (16.6 g, 22 mmol), 58-6 (4.4 g, 22 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 58-7 (13.5 g, 74% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 77.79; H, 3.99; N, 6.72; Measured C, 77.81; H, 3.99; N, 6.70. Mass spectrometry: Theoretical 832.18; Measured 832.1 (M+).

[0634] Under an argon atmosphere, 58-7 (9.2 g, 11 mmol), 58-8 (3.3 g, 11 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 58-9 (8.4 g, 76% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 80.87; H, 4.09; N, 5.55; Measured C, 80.91; H, 4.05; N, 5.58. Mass spectrometry: Theoretical 1008.25; Measured 1008.2 (M+).

[0635] Under an argon atmosphere, 58-9 (7.6 g, 7.5 mmol), pinacol diborate (8.9 g, 35 mmol), potassium acetate (3.4 g, 35 mmol), dioxane (120 mL), and Pd(dppf)Cl2 (0.5 g, 0.7 mmol) were added to a 250 mL round-bottom flask and heated to reflux for 12 hours. After the reaction was complete, the mixture was cooled, the solvent was removed, and the product was hydrolyzed with an aqueous sodium hydroxide solution. The product was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain compound 58-10 (5.9 g, 81% yield). Elemental analysis: Theoretical C, 83.78; H, 4.45; N, 5.75; Measured C, 83.81; H, 4.46; N, 5.73. Mass spectrometry: Theoretical 974.34; Measured 974.3 (M+).

[0636] Under an argon atmosphere, 58-10 (4.9 g, 5 mmol), 58-7 (4.2 g, 5 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound H-142 (6.6 g, 75% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 87.02; H, 4.43; N, 6.65; Measured C, 87.00; H, 4.46; N, 6.64. Mass spectrometry: Theoretical 1682.59; Measured 1682.5 (M+).

[0637] Example 59

[0638] The reaction is as follows:

[0639]

[0640] Under an argon atmosphere, 59-1 (13.6 g, 40 mmol), 59-2 (14.7 g, 80 mmol), 19.0 g sodium metabisulfite (100 mmol), and N,N-dimethylformamide (140 mL) were added to a 250 mL round-bottom flask, and the mixture was heated and stirred at 100 °C for 10 hours. After the reaction solution cooled to room temperature, it was poured into cold water and extracted three times with ethyl acetate (3 × 50 mL). The organic phase was separated, and the product compound 59-3 (20.8 g, 78% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical value C, 57.59; H, 3.02; N, 8.40; Measured value C, 57.53; H, 3.00; N, 8.28. Mass spectrometry: Theoretical value 665.99; Measured value 665.9 (M+).

[0641] Under an argon atmosphere, 59-3 (20.0 g, 30 mmol), 59-4 (8.3 g, 30 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 59-5 (17.1 g, 74% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 73.06; H, 3.91; N, 12.69; Measured C, 73.04; H, 3.91; N, 12.66. Mass spectrometry: Theoretical 771.17; Measured 771.1 (M+).

[0642] Under an argon atmosphere, 59-5 (16.2 g, 21 mmol), 59-6 (4.2 g, 21 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 59-7 (13.7 g, 77% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 75.00; H, 4.04; N, 11.55; Measured C, 75.02; H, 4.01; N, 11.58. Mass spectrometry: Theoretical 847.21; Measured 847.2 (M+).

[0643] Under an argon atmosphere, 59-7 (9.3 g, 11 mmol), 59-8 (3.3 g, 11 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 59-9 (8.3 g, 74% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 78.51; H, 4.13; N, 9.57; Measured C, 78.50; H, 4.14; N, 9.52. Mass spectrometry: Theoretical 1023.27; Measured 1023.2 (M+).

[0644] Under an argon atmosphere, 59-9 (7.7 g, 7.5 mmol), pinacol diborate (8.9 g, 35 mmol), potassium acetate (3.4 g, 35 mmol), dioxane (120 mL), and Pd(dppf)Cl2 (0.5 g, 0.7 mmol) were added to a 250 mL round-bottom flask and heated to reflux for 12 hours. After the reaction was complete, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The product was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain compound 59-10 (5.9 g, 80% yield). Elemental analysis: Theoretical C, 81.29; H, 4.48; N, 9.90; Measured C, 81.92; H, 4.44; N, 9.97. Mass spectrometry: Theoretical 989.36; Measured 989.3 (M+).

[0645] Under an argon atmosphere, 59-10 (4.9 g, 5 mmol), 59-7 (4.2 g, 5 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound H-143 (6.6 g, 77% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical value C, 84.09; H, 4.47; N, 11.44; Measured value C, 84.12; H, 4.46; N, 11.48. Mass spectrometry: Theoretical value 1712.64; Measured value 1712.6 (M+).

[0646] Example 60

[0647] The reaction is as follows:

[0648]

[0649] Under an argon atmosphere, 60-1 (13.6 g, 40 mmol), 60-2 (14.7 g, 80 mmol), 19.0 g sodium metabisulfite (100 mmol), and N,N-dimethylformamide (140 mL) were added to a 250 mL round-bottom flask. The mixture was heated and stirred at 100 °C for 10 hours. After the reaction solution cooled to room temperature, it was poured into cold water and extracted three times with ethyl acetate (3 × 50 mL). The organic phase was separated, and the product compound 60-3 (20.5 g, 77% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical value C, 57.59; H, 3.02; N, 8.40; Measured value C, 57.56; H, 3.03; N, 8.24. Mass spectrometry: Theoretical value 665.99; Measured value 665.9 (M+).

[0650] Under an argon atmosphere, 60-3 (20.0 g, 30 mmol), 60-4 (8.6 g, 30 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 60-5 (17.6 g, 75% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 76.72; H, 5.92; N, 7.16; Measured C, 76.70; H, 5.95; N, 7.17. Mass spectrometry: Theoretical 781.27; Measured 781.2 (M+).

[0651] Under an argon atmosphere, 60-5 (16.4 g, 21 mmol), 60-6 (4.2 g, 21 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 60-7 (14.0 g, 78% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 78.31; H, 5.86; N, 6.52; Measured C, 78.32; H, 5.88; N, 6.57. Mass spectrometry: Theoretical 857.30; Measured 857.3 (M+).

[0652] Under an argon atmosphere, 60-7 (9.4 g, 11 mmol), 60-8 (3.3 g, 11 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 60-9 (8.4 g, 74% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 81.22; H, 5.65; N, 5.41; Measured C, 81.26; H, 5.61; N, 5.40. Mass spectrometry: Theoretical 1033.36; Measured 1033.3 (M+).

[0653] Under an argon atmosphere, 60-9 (7.8 g, 7.5 mmol), pinacol diborate (8.9 g, 35 mmol), potassium acetate (3.4 g, 35 mmol), dioxane (120 mL), and Pd(dppf)Cl2 (0.5 g, 0.7 mmol) were added to a 250 mL round-bottom flask and heated to reflux for 12 hours. After the reaction was complete, the mixture was cooled, the solvent was removed, and the product was hydrolyzed with an aqueous sodium hydroxide solution. The solution was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to give compound 60-10 (6.1 g, 81% yield). Elemental analysis: Theoretical C, 84.07; H, 6.05; N, 5.60; Measured C, 84.11; H, 6.02; N, 5.64. Mass spectrometry: Theoretical 999.46; Measured 999.4 (M+).

[0654] Under an argon atmosphere, 60-10 (5.0 g, 5 mmol), 60-7 (4.3 g, 5 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound H-144 (6.5 g, 74% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 87.26; H, 6.27; N, 6.46; Measured C, 87.31; H, 6.27; N, 6.43. Mass spectrometry: Theoretical 1732.83; Measured 1732.8 (M+).

[0655] Example 61

[0656] The reaction is as follows:

[0657]

[0658] Under an argon atmosphere, 61-1 (12.4 g, 40 mmol), 61-2 (7.4 g, 40 mmol), 15.2 g sodium metabisulfite (80 mmol), and N,N-dimethylformamide (100 mL) were added to a 250 mL round-bottom flask. The mixture was heated and stirred at 100 °C for 10 hours. After the reaction solution cooled to room temperature, it was poured into cold water and extracted three times with ethyl acetate (3 × 50 mL). The organic phase was separated, and the product compound 61-3 (14.8 g, 78% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical value C, 48.03; H, 2.55; N, 5.90; Measured value C, 48.02; H, 2.57; N, 5.88. Mass spectrometry: Theoretical value 473.92; Measured value 473.9 (M+).

[0659] Under an argon atmosphere, 61-3 (14.2 g, 30 mmol), 61-4 (8.2 g, 30 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 61-5 (13.3 g, 77% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 76.95; H, 4.36; N, 4.85; Measured C, 76.97; H, 4.34; N, 4.81. Mass spectrometry: Theoretical 576.12; Measured 576.1 (M+).

[0660] Under an argon atmosphere, 61-5 (12.7 g, 22 mmol), 61-6 (4.4 g, 22 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 61-7 (10.5 g, 73% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 79.02; H, 4.47; N, 4.29; Measured C, 79.07; H, 4.45; N, 4.23. Mass spectrometry: Theoretical 652.15; Measured 652.1 (M+).

[0661] Under an argon atmosphere, 61-8 (13.6 g, 40 mmol), 61-2 (14.7 g, 80 mmol), 19.0 g sodium metabisulfite (100 mmol), and N,N-dimethylformamide (140 mL) were added to a 250 mL round-bottom flask, and the mixture was heated and stirred at 100 °C for 10 hours. After the reaction solution cooled to room temperature, it was poured into cold water and extracted three times with ethyl acetate (3 × 50 mL). The organic phase was separated, and the product compound 61-9 (20.5 g, 77% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical value C, 57.59; H, 3.02; N, 8.40; Measured value C, 57.51; H, 3.06; N, 8.27. Mass spectrometry: Theoretical value 665.99; Measured value 665.9 (M+).

[0662] Under an argon atmosphere, 61-9 (20.0 g, 30 mmol), 61-4 (8.2 g, 30 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 61-10 (17.1 g, 74% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 78.02; H, 4.32; N, 7.28; Measured C, 78.00; H, 4.34; N, 7.23. Mass spectrometry: Theoretical 768.19; Measured 768.1 (M+).

[0663] Under an argon atmosphere, 61-10 (16.1 g, 21 mmol), 61-6 (4.2 g, 21 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 61-11 (13.3 g, 75% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 79.52; H, 4.41; N, 6.62; Measured C, 79.56; H, 4.43; N, 6.59. Mass spectrometry: Theoretical 844.22; Measured 844.2 (M+).

[0664] Under an argon atmosphere, 61-11 (12.7 g, 15 mmol), 61-12 (4.5 g, 15 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 61-13 (11.3 g, 74% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 82.26; H, 4.44; N, 5.48; Measured C, 82.24; H, 4.49; N, 5.44. Mass spectrometry: Theoretical 1020.28; Measured 1020.2 (M+).

[0665] Under an argon atmosphere, 61-13 (10.7 g, 10.5 mmol), pinacol diborate (8.9 g, 35 mmol), potassium acetate (3.4 g, 35 mmol), dioxane (120 mL), and Pd(dppf)Cl2 (0.5 g, 0.7 mmol) were added to a 250 mL round-bottom flask and heated to reflux for 12 hours. After the reaction was complete, the mixture was cooled, the solvent was removed, and the product was hydrolyzed with an aqueous sodium hydroxide solution. The solution was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain compound 61-14 (8.1 g, 78% yield). Elemental analysis: Theoretical value C, 85.19; H, 4.80; N, 5.68; Measured value C, 85.22; H, 4.85; N, 5.69. Mass spectrometry: Theoretical value 986.38; Measured value 986.3 (M+).

[0666] Under an argon atmosphere, 61-14 (6.9 g, 7 mmol), 61-7 (4.6 g, 7 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound H-145 (8.2 g, 77% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 89.54; H, 4.92; N, 5.54; Measured C, 89.56; H, 4.93; N, 5.51. Mass spectrometry: Theoretical 1514.60; Measured 1514.6 (M+).

[0667] Example 62

[0668] The reaction is as follows:

[0669]

[0670] Under an argon atmosphere, 62-1 (13.6 g, 40 mmol), 62-2 (14.7 g, 80 mmol), 19.0 g sodium metabisulfite (100 mmol), and N,N-dimethylformamide (140 mL) were added to a 250 mL round-bottom flask, and the mixture was heated and stirred at 100 °C for 10 hours. After the reaction solution cooled to room temperature, it was poured into cold water and extracted three times with ethyl acetate (3 × 50 mL). The organic phase was separated, and the product compound 62-3 (20.8 g, 78% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical value C, 57.59; H, 3.02; N, 8.40; Measured value C, 57.51; H, 3.00; N, 8.24. Mass spectrometry: Theoretical value 665.99; Measured value 665.9 (M+).

[0671] Under an argon atmosphere, 62-3 (20.0 g, 30 mmol), 62-4 (7.9 g, 30 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 62-5 (17.0 g, 75% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 76.09; H, 3.86; N, 7.39; Measured C, 76.11; H, 3.83; N, 7.43. Mass spectrometry: Theoretical 756.15; Measured 756.1 (M+).

[0672] Under an argon atmosphere, 62-5 (10.6 g, 14 mmol), 62-6 (4.2 g, 14 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL), and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed three times with deionized water. The organic phase was separated, and the product compound 62-7 (9.7 g, 74% yield) was obtained by column chromatography and solvent removal. Elemental analysis: Theoretical C, 79.74; H, 3.99; N, 6.00; Measured C, 79.77; H, 3.97; N, 6.03. Mass spectrometry: Theoretical 932.22; Measured 932.2 (M+).

[0673] Under an argon atmosphere, 62-7 (8.9 g, 9.5 mmol), pinacol diborate (8.9 g, 35 mmol), potassium acetate (3.4 g, 35 mmol), dioxane (120 mL), and Pd(dppf)Cl2 (0.5 g, 0.7 mmol) were added to a 250 mL round-bottom flask and heated to reflux for 12 hours. After the reaction was complete, the mixture was cooled, the solvent was removed, and the product was hydrolyzed with an aqueous sodium hydroxide solution. The product was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain compound 62-8 (7.0 g, 82% yield). Elemental analysis: Theoretical C, 82.85; H, 4.37; N,...

Claims

1. An anthracene compound, characterized in that, It has one of the structures of type H-1 to type H-195; 。 2. The method for preparing the anthracene compound according to claim 1, characterized in that, Includes the following steps: S1) Reacting a compound having the structure of Formula 6 with a compound having the structure of Formula 7 yields a compound having the structure of Formula 8; Formula 6; Formula 7; Formula 8; Wherein, y is 1 or 2; X1 and X2 independently comprise either Cl or Br; Ar1 and Ar2 independently include one of the groups having the structures shown in Formula A-1 to Formula A-32; ； S2) The compound having the structure of formula 8 from step S1) is boronized and then reacted with the compound having the structure of formula 9 to obtain the anthracene compound; Equation 9; Where x is 1 or 2; The z is 0 or 1; X3 includes Cl or Br; The Ar5 and Ar6 independently include one of the groups having the structure of formula a-1 to a-25: ； R1 and R3 independently include one of the groups having the structure of formula R-1 to formula R-48; Wherein, D is a deuterium atom that replaces the hydrogen atom on the aryl group attached thereto, n represents the number of substitutions, and n is an integer from 0 to 13.

3. An electroluminescent device, characterized in that, It includes an anode, a cathode, and an organic thin film layer located between the anode and the cathode; the organic thin film layer includes the anthracene compound of claim 1.

4. The application of the anthracene compounds of claim 1 as electron transport host materials in flat panel display devices, flexible display devices, or lighting sources.

Images