1, 2-dihydrobenzo-silacyclohexane compound as well as preparation method and application thereof

Abstract

The invention discloses a 1, 2-dihydrobenzo silacyclohexane compound and a preparation method and application thereof, and discloses a preparation method for synthesizing two silicon-containing six-membered ring compounds with different substituent positions in one step by starting from the same raw material and controlling reaction conditions. A complex formed by a metal catalyst palladium salt and a phosphine ligand is used as a catalyst precursor, the chemical selectivity of a product is controlled by changing the structure of the ligand, and a series of silicon-containing six-membered ring compounds with high yield and high chemical selectivity are efficiently synthesized through intermolecular cycloaddition reaction. Compared with traditional cycloaddition and other reactions, the method for synthesizing the naphthenic compound is more efficient, direct and effective, various silicon heterocyclic compounds with different substituent groups, which cannot be prepared by a traditional method, can be obtained, and the method is widely applied to the fields of material chemistry and pharmaceutical chemistry.

Description

Technical Field

[0001] The present invention relates to the field of organic chemistry, and particularly relates to a 1,2-dihydrobenzodisilacyclohexane compound, a preparation method thereof and an application thereof. Background Art

[0002] In recent years, chiral organosilanes have gradually played an important role in silicon substitution in organic synthesis, materials science and medicinal chemistry. Compounds with silicon substitution have received increasing attention in medicinal chemistry due to their low toxicity and favorable metabolic characteristics. Among them, organic compounds containing silacycle structures have become very useful synthetic building blocks in organic chemistry and are an important part of selective carbon-carbon bond formation. Their construction methods usually involve cyclization reactions of chain silanes, but such methods are not universal, and some ideal silacycle structures are difficult to construct. Instead, using the high ring strain of small silicon-containing rings to achieve a series of ring-opening and ring-expansion reactions to construct different structural silacycle molecules has good generality. Among them, silacyclobutane (SCB) is the most promising organic small molecule building block. Since Sommer and Baum pioneered the synthesis of SCB, a series of SCB ring-expansion reactions have been developed using its high ring strain and Lewis acidity. The cycloaddition reaction provides a direct route for constructing chiral organosilacycle structures. However, due to the difficulty in distinguishing the chemoselectivity in internal alkyne substrates, the selective Si-C bond cleavage of benzosilacyclobutane remains a challenge.

[0003] Researchers have increasingly focused on developing effective and selective construction methods for these important building blocks. Generally, researchers use the ring-opening and ring-expansion reactions of silacyclobutane with various unsaturated alkynes or alkenes to construct a series of different structural silacycle molecules, and preliminary attempts have been made for the construction of silicon chirality. These research progress show that transition metal catalysts can effectively activate the Si-C bond of silacyclobutane to achieve a series of ring-opening and ring-expansion reactions to construct different structural silacycle molecules, providing silacycle functional structures with significant application prospects for drug research and development. However, the existing synthesis methods have obvious limitations: firstly, the reaction specificity is too strong, and only specific types of heterocyclic ring skeletons can be constructed; secondly, the reaction efficiency is low, and the typical yields are generally low. Summary of the Invention

[0004] The purpose of the present invention is to solve the problems such as the low efficiency of previous synthesis methods and the difficulty in obtaining benzodisilacyclohexane compounds with different substituents, and to provide a 1,2-dihydrobenzodisilacyclohexane compound, a preparation method thereof and an application thereof.

[0005] The present invention is achieved by the following technical solutions:

[0006] In a first aspect, the present invention provides a 1,2-dihydrobenzodisilacyclohexane compound, which has a structural formula shown in the following formula (I) or formula (II):

[0007]

[0008] In the formula, R1 is one of hydrogen, alkyl, halogenated group (including halogen or haloalkyl), alkoxy or phenyl.

[0009] In a second aspect, the present invention provides a preparation method of the above 1,2-dihydrobenzodisilacyclohexane compound. The reaction conditions are mild and the method is simple, and high-yield benzodisilacyclohexane compounds with various different substituents can be obtained in one step. The preparation method is to synthesize 1,2-dihydrobenzodisilacyclohexane compounds with two different substituent positions by the cycloaddition silanization reaction of benzodisilacyclobutane and phenylpropiolaldehyde. The reaction formula is as follows:

[0010]

[0011] The specific reaction steps are as follows: under an inert gas atmosphere, a phosphine ligand, a palladium metal catalyst, an additive and a reaction medium are added to a reaction tube. After stirring for 10-20 min, a phenylpropiolaldehyde compound 1 and a benzodisilacyclobutane 2 are added in sequence. After reacting for a certain time, sodium borohydride is directly added for reduction. After the reaction is completed, the solvent is evaporated to obtain a crude product, and the crude product is separated and purified to obtain the 1,2-dihydrobenzodisilacyclohexane compound.

[0012] The molar ratio of the phenylpropiolaldehyde compound to the benzodisilacyclobutane is 1:2 to 1:3. Preferably, the concentration of the phenylpropiolaldehyde compound as a reactant is 0.1 mol / L. The phenylpropiolaldehyde compound and the benzodisilacyclobutane as reactants directly carry out a selective cycloaddition silane reaction under the action of a complex formed by a metal catalyst and a phosphine ligand. The reaction is easy to synthesize, the operation is simple, and the obtained crude product can be concentrated under reduced pressure after removing impurities by flash column chromatography to obtain a pure product, and the post-treatment is convenient.

[0013] Preferably, the palladium metal catalyst is bis(dibenzylideneacetone)palladium(0), and the usage amount is 3-6% of the molar amount of the phenylpropiolaldehyde compound.

[0014] Preferably, the phosphine ligand is selected from one of triphenylphosphine, tris(4-methylphenyl)phosphine or tricyclohexylphosphine tetrafluoroborate, and more preferably tris(4-methylphenyl)phosphine or tricyclohexylphosphine tetrafluoroborate.

[0015] Preferably, the usage amount of the phosphine ligand is 10-12% of the molar amount of the phenylpropiolaldehyde compound. A complex formed by a metal catalyst and a phosphine ligand is used as a catalyst precursor, and the catalytic efficiency is good, and a high-yield target product can be obtained.

[0016] Preferably, the reaction medium is selected from one of n-hexane, toluene, dichloromethane, dichloroethane, and diethyl ether. A mixed solvent composed of two solvents selected from n-hexane, dichloromethane, dichloroethane, and diethyl ether can also be used as the solvent. For example, a solvent mixture of n-hexane and dichloromethane, or n-hexane and dichloroethane. The amount used is such that the solute can react fully. More preferably, it is toluene.

[0017] Preferably, the reaction temperature is 10 - 40 °C and the reaction time is 10 - 24 h.

[0018] In a third aspect, the present invention provides the application of the above 1,2-dihydrobenzodisilacyclohexane compound as a luminescent material. The disilacyclopentadiene structure therein provides a new direction for the research and development of luminescent materials due to its unique electronic properties.

[0019] In a fourth aspect, the present invention provides the application of the above 1,2-dihydrobenzodisilacyclohexane compound as a drug synthesis precursor.

[0020] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0021] The present invention uses an easily prepared asymmetric phenylpropiolaldehyde as the raw material, and a complex formed by a metal catalyst palladium salt and a phosphine ligand as the catalyst precursor. The catalyst precursor participates in the catalytic cycle system, with relatively high catalytic efficiency. An additive is used to control the chemoselectivity of the product, and a target product with extremely high yield can be obtained. A series of 1,2-dihydrobenzodisilacyclohexane compounds are efficiently synthesized through an intermolecular cycloaddition silanization reaction. The catalyst precursor is a commercial reagent, and the reaction can be completed by stirring at a relatively low temperature. The operation is simple and the yield is relatively high. The crude product can be concentrated under reduced pressure after removing impurities by flash column chromatography, and the post-treatment is convenient. It is a more direct and effective method for synthesizing silacycle compounds compared with the traditional chain-like silane cyclization reaction, and various benzodisilacyclohexane compounds with different substituents that cannot be prepared by traditional methods can be obtained. It can be widely applied in the fields of materials chemistry and pharmaceutical chemistry. For example, derivatives shown in the following formula can be widely applied in the fields of materials chemistry and pharmaceutical chemistry:

[0022]

[0023] The following further elaborates the present invention in conjunction with examples. All raw materials used in the examples are commercially available or can be prepared by conventional methods. Description of the Drawings

[0024] Figure 1 1H NMR spectrum of the chiral center cyclopropylsilane compound prepared in Example 1;

[0025] Figure 2 13C NMR spectrum of the chiral center cyclopropylsilane compound prepared in Example 1;

[0026] Figure 3 1H NMR spectrum of the bicyclic chiral center cyclopropylsilane compound prepared in Example 2;

[0027] Figure 4 13C NMR spectrum of the bicyclic chiral center cyclopropylsilane compound prepared in Example 2;

[0028] Figure 5 1H NMR spectrum of the bicyclic chiral center cyclopropylsilane compound prepared in Example 21;

[0029] Figure 6 13C NMR spectrum of the bicyclic chiral center cyclopropylsilane compound prepared in Example 21. Detailed implementation mode

[0030] The present invention will be further described in detail below with reference to examples. All raw materials used in the examples can be purchased commercially or prepared by conventional methods.

[0031] As described above, the present invention provides a method for preparing a class of 1,2-dihydrobenzisosilacyclohexane compounds with different substituent positions by Pd-catalyzed highly selective cycloaddition silylation of phenylpropiolaldehyde, as well as the scope expansion of phenylpropiolaldehyde derivatives. Its isosilacyclohexane structure is similar to drugs such as silteplase and vinflunine, and has important application value in reducing drug toxicity and drug sustained release. It also provides a feasible solution for the application of the silteplase strategy of other drug molecules with a cyclohexane skeleton.

[0032] Specifically, the structural formula of the 1,2-dihydrobenzisosilacyclohexane compound is shown as follows:

[0033]

[0034] Wherein R and R' are respectively selected from And the two are different; R1 is one of hydrogen, alkyl, halogenated group (including halogen or halogenated alkyl), alkoxy or phenyl.

[0035] The 1,2-dihydrobenzisosilacyclohexane compound is prepared by the following method:

[0036] Under an inert gas atmosphere, a phosphine ligand, a metal palladium catalyst bis(dibenzylideneacetone)palladium(0), an additive, and a reaction medium are added to a reaction tube. After stirring for 10-20 min, a phenylpropiolaldehyde compound 1 and a benzisosilacyclobutane 2 with a molar ratio of 1:2 to 1:3 are added in sequence. After reacting at 10-40 °C for 10-24 h, sodium borohydride is directly added for reduction. After the reaction is completed, the solvent is evaporated to obtain a crude product, and the crude product is separated and purified to obtain the 1,2-dihydrobenzisosilacyclohexane compound.

[0037] The reaction medium is selected from one of n-hexane, toluene, dichloromethane, dichloroethane, and diethyl ether, or a mixed solvent composed of two solvents selected from n-hexane, dichloromethane, dichloroethane, and diethyl ether can also be chosen as the solvent, such as: n-hexane and dichloromethane solvents, n-hexane and dichloroethane solvents, etc. The usage amount is the amount that enables the solute to react fully.

[0038] The phosphine ligand is selected from one of triphenylphosphine (L1), tris(4-methylphenyl)phosphine (L2), and tricyclohexylphosphine tetrafluoroborate (L3), and more preferably tris(4-methylphenyl)phosphine or tricyclohexylphosphine tetrafluoroborate.

[0039]

[0040] The following further illustrates the present invention in conjunction with specific embodiments.

[0041] Example 1:

[0042] Under a nitrogen atmosphere, add the phosphine ligand L2 tris(4-methylphenyl)phosphine (6.1 mg, 0.02 mmol) and the metal catalyst bis(dibenzylideneacetone)palladium (5.7 mg, 0.01 mmol) to a Schlenk reaction tube, then add 2.0 mL of toluene solvent. After pre-stirring at 30 °C for 10 min, add the phenylpropiolaldehyde compound 1a (0.20 mmol). After stirring for 15 min, add benzosilacyclobutane (0.4 mmol). Continue to stir and react at 30 °C for 10 h. After monitoring the reaction by TLC and it is completed, directly add sodium borohydride and methanol for reduction, then filter, extract, concentrate the filtrate, and purify it by silica gel column chromatography to obtain 45 mg of a pale yellow oily liquid product 3a with a yield of 80%. Its 1H NMR spectrum is as Figure 1 shown, and its 13C NMR spectrum is as Figure 2 shown.

[0043]

[0044] The physical and chemical indexes of this product: 1 , , 13 ,

[0045] H NMR (400 MHz, CDCl3) δ 7.34–7.20 (m, 3H), 7.12–7.02 (m, 3H), 6.97 (t, J = 7.4 Hz, 1H), 6.85 (t, J = 7.6 Hz, 1H), 6.59 (d, J = 7.9 Hz, 1H), 4.08 (s, 2H), 2.14 (s, 2H), 1.36 (b, 1H), 0.15 (s, 6H).

[0045] 1313C NMR (101 MHz, CDCl3) δ 150.2, 140.1, 137.0, 136.1, 135.3, 130.3, 128.8, 128.0, 127.4, 126.0, 125.8, 124.1, 62.9, 20.4, -4.4.

[0046] HRMS (ESI) m / z: [M+Na] + calculated for C 18 H 20 NaOSi: 303.1176, found: 303.1175.

[0047] Example 2:

[0048] Under a nitrogen atmosphere, add the phosphine ligand L2 tris(4-methylphenyl)phosphine (6.1 mg, 0.02 mmol) and the metal catalyst bis(dibenzylideneacetone)palladium (2.7 mg, 0.006 mmol) to a Schlenk reaction tube. Then add 2.0 mL of n-hexane solvent. After pre-stirring at 30 °C for 10 min, add the phenylpropiolaldehyde compound 1b (0.20 mmol). After stirring for 15 min, add benzosilacyclobutane (0.6 mmol). Continue stirring the reaction at 30 °C for 20 h. After monitoring the reaction by TLC and it is completed, directly add sodium borohydride and methanol for reduction. Then filter, extract, concentrate the filtrate, and purify it by silica gel column chromatography to obtain 35 mg of a pale yellow oily liquid product 3b with a yield of 60%. Its 1H NMR spectrum is as Figure 3 shown, and its 13C NMR spectrum is as Figure 4 shown.

[0049]

[0050] The physical and chemical indexes of this product are: 1 1H NMR (400 MHz, CDCl3) δ 7.24 (d, J = 7.7 Hz, 2H), 7.20 (d, J = 7.5 Hz, 1H), 7.14–7.02 (m, 3H), 6.98 (d, J = 15.1 Hz, 1H), 6.75 (d, J = 7.8 Hz, 1H), 4.22 (s, 2H), 2.43 (s, 3H), 2.26 (s, 2H), 1.59 (b, 1H), 0.27 (s, 6H).

[0051] 13 13C NMR (101 MHz, CDCl3) δ 151.3, 138.3, 138.2, 137.1, 136.5, 136.5, 131.4, 130.0, 129.2, 129.0, 127.1, 125.2, 64.0, 21.6, 21.3, -3.3.

[0052] HRMS(ESI) m / z: [M+Na] + calculated for C 19 H 22 NaOSi: 317.1332, found: 317.1332.

[0053] Example 3:

[0054] Under a nitrogen atmosphere, triphenylphosphine (6.0 mg, 0.024 mmol) of phosphine ligand L1 and bis(dibenzylideneacetone)palladium (5.7 mg, 0.01 mmol) of metal catalyst were added to a Schlenk reaction tube, and then 2.0 mL of dichloromethane solvent was added. After pre-stirring at 30 °C for 20 min, propargyl aldehyde compound 1c (0.20 mmol) was added. After stirring for 15 min, benzosilacyclobutane (0.6 mmol) was added, and the reaction was continued to stir at 30 °C for 20 h. After monitoring the reaction by TLC and completion, sodium borohydride and methanol were directly added for reduction, then filtered, extracted, the filtrate was concentrated, and purified by silica gel column chromatography to obtain 48 mg of a pale yellow oily liquid product 3c with a yield of 77%.

[0055]

[0056] The physical and chemical indexes of this product: 1 H NMR (400 MHz, CDCl3) δ 7.08 (d, J = 7.6 Hz, 1H), 7.02–6.94 (m, 3H), 6.92–6.81 (m, 3H), 6.64 (d, J = 7.8 Hz, 1H), 4.12 (s, 2H), 3.77 (s, 3H), 2.14 (s, 2H), 1.42 (b, 1H), 0.15 (s, 6H).

[0057] 13 C NMR (101 MHz, CDCl3) δ 158.4, 151.1, 138.4, 137.3, 136.5, 133.2, 131.3, 130.2, 129.9, 127.1, 125.1, 113.8, 63.9, 55.3, 21.5, -3.3.

[0058] HRMS(ESI) m / z: [M+Na] + calculated for C 19 H 22 NaO2Si: 333.1281, found: 333.1283.

[0059] Example 4:

[0060] Under a nitrogen atmosphere, add the phosphine ligand L2 tris(4-methylphenyl)phosphine (6.1 mg, 0.02 mmol) and the metal catalyst bis(dibenzylideneacetone)palladium (5.7 mg, 0.01 mmol) to a Schlenk reaction tube. Then add 2.0 mL of toluene solvent. After pre-stirring at 30 °C for 10 min, add the phenylpropiolaldehyde compound 1d (0.20 mmol). After stirring for 15 min, add benzosilacyclobutane (0.6 mmol). Continue to stir the reaction at 30 °C for 20 h. After monitoring the reaction by TLC until it is completed, directly add sodium borohydride and methanol for reduction. Then filter, extract, concentrate the filtrate, and purify it by silica gel column chromatography to obtain 36 mg of the product 3d as a pale yellow oily liquid, with a yield of 60%.

[0061]

[0062] The physical and chemical indexes of this product are as follows: 1 H NMR (400 MHz, CDCl3) δ 7.11–7.07 (m, 1H), 7.03–6.96 (m, 5H), 6.87 (td, J = 7.6, 1.5 Hz, 1H), 6.56 (dd, J = 7.9, 1.4 Hz, 1H), 4.09 (s, 2H), 2.14 (s, 2H), 1.39 (b, 1H), 0.15 (s, 6H).

[0063] 19 F NMR (376 MHz, CDCl3) δ -115.56.

[0064] 13 C NMR (101 MHz, CDCl3) δ 160.7 (d, J = 245.6 Hz), 149.1, 136.8 (d, J = 9.2 Hz), 135.9 (d, J = 3.6 Hz), 135.4, 130.3, 129.6, 129.6, 128.7, 126.2, 124.1, 114.3 (d, J = 21.4 Hz), 62.8, 20.4, -4.4.

[0065] HRMS (ESI) m / z: [M+Na] + calculated for C 24 H 24 NaFOSi: 321.1081, found: 321.1084.

[0066] Example 5:

[0067] Under a nitrogen atmosphere, add the phosphine ligand L2 tris(4-methylphenyl)phosphine (6.1 mg, 0.02 mmol) and the metal catalyst bis(dibenzylideneacetone)palladium (5.7 mg, 0.01 mmol) to a Schlenk reaction tube. Then add 2.0 mL of toluene solvent. After pre-stirring at 30 °C for 10 min, add the phenylpropiolaldehyde compound 1e (0.20 mmol). After stirring for 15 min, add benzosilacyclobutane (0.6 mmol). Continue stirring the reaction at 30 °C for 24 h. After monitoring the reaction by TLC until it is completed, directly add sodium borohydride and methanol for reduction. Then filter, extract, concentrate the filtrate, and purify it by silica gel column chromatography to obtain 48 mg of a pale yellow oily liquid product 3e with a yield of 76%.

[0068]

[0069] The physical and chemical indicators of this product are as follows: 1 H NMR (400 MHz, CDCl3) δ 7.32–7.25 (m, 2H), 7.10–7.06 (m, 1H), 7.00–6.95 (m, 3H), 6.90–6.84 (m, 1H), 6.55 (dd, J = 7.9, 1.4 Hz, 1H), 4.08 (s, 2H), 2.13 (s, 2H), 1.52 (b, 1H), 0.14 (s, 6H).

[0070] 13 C NMR (101 MHz, CDCl3) δ 148.8, 138.5, 136.8, 136.6, 135.4, 131.7, 130.4, 129.4, 128.7, 127.6, 126.2, 124.1, 62.8, 20.4, -4.4.

[0071] HRMS (ESI) m / z: [M+Na] + calculated for C 18 H 19 NaClOSi: 337.0786, found: 337.0782.

[0072] Example 6:

[0073] Under a nitrogen atmosphere, the phosphine ligand L2 tris(4-methylphenyl)phosphine (6.1 mg, 0.02 mmol) and the metal catalyst bis(dibenzylideneacetone)palladium (5.7 mg, 0.01 mmol) were added to a Schlenk reaction tube. Then, 2.0 mL of toluene solvent was added. After pre-stirring at 30 °C for 10 min, the propargyl aldehyde compound 1f (0.20 mmol) was added. After stirring for 15 min, benzosilacyclobutane (0.6 mmol) was added, and the reaction was continued to stir at 30 °C for 20 h. After monitoring the reaction by TLC until completion, sodium borohydride and methanol were directly added for reduction. Then, filtration, extraction were carried out, and the filtrate was concentrated and purified by silica gel column chromatography to obtain 40 mg of a pale yellow oily liquid product 3f with a yield of 60%.

[0074]

[0075] The physical and chemical indexes of this product are as follows: 1 H NMR (400 MHz, CDCl3) δ 7.30 (d, J = 8.2 Hz, 1H), 7.10–7.04 (m, 1H), 7.00–6.93 (m, 3H), 6.89–6.83 (m, 1H), 6.64–6.60 (m, 1H), 4.08 (s, 2H), 2.13 (s, 2H), 1.54 (s, 2H), 1.27 (s, 6H), 0.14 (s, 4H).

[0076] 13 C NMR (101 MHz, CDCl3) δ 150.5, 148.5, 137.2, 136.9, 135.9, 135.3, 130.2, 128.9, 127.6, 125.9, 124.2, 124.0, 62.9, 33.5, 30.4, 20.4, -4.4.

[0077] HRMS (ESI) m / z: [M+Na] + calculated for C 22 H 28 NaOSi: 359.1802, found: 359.1798.

[0078] Example 7:

[0079] Under a nitrogen atmosphere, add the phosphine ligand L2 tris(4-methylphenyl)phosphine (6.1 mg, 0.02 mmol) and the metal catalyst bis(dibenzylideneacetone)palladium (5.7 mg, 0.01 mmol) to a Schlenk reaction tube. Then add 2.0 mL of toluene solvent. After pre-stirring at 30 °C for 10 min, add 1 g (0.20 mmol) of the phenylpropiolaldehyde compound. After stirring for 15 min, add benzosilacyclobutane (0.6 mmol). Continue stirring the reaction at 30 °C for 20 h. After monitoring the reaction by TLC and it is completed, directly add sodium borohydride and methanol for reduction. Then filter, extract, concentrate the filtrate, and purify by silica gel column chromatography to obtain 52 mg of the pale yellow oily liquid product 3g, with a yield of 73%.

[0080]

[0081] The physical and chemical indexes of this product are as follows: 1 H NMR(400MHz,CDCl3)δ7.55(t,J=7.6Hz,4H),7.37(t,J=7.6Hz,2H),7.31–7.23(m,1H),7.10(t,J=8.0Hz,3H),7.03–6.95(m,1H),6.88(td,J=7.6,1.5Hz,1H),6.67(dd,J=7.9,1.4Hz,1H),4.15(s,2H),2.16(s,2H),1.58(b,1H),0.17(s,6H).

[0082] 13 C NMR(101MHz,CDCl3)δ150.0,139.7,139.1,138.6,137.0,136.3,135.4,130.3,128.9,128.5,127.8,126.3,126.1,126.1,126.0,124.1,62.9,20.4,-4.4.

[0083] HRMS(ESI)m / z:[M+Na] + calculated for C 22 H 26 NaOSi:379.1489,found:379.1487.

[0084] Example 8:

[0085] Under a nitrogen atmosphere, triphenylphosphine (6.1 mg, 0.02 mmol) and bis(dibenzylideneacetone)palladium (5.7 mg, 0.01 mmol) were added to a Schlenk reaction tube. Then, 2.0 mL of toluene was added as the solvent. After pre-stirring at 30 °C for 10 min, propargyl aldehyde compound 1h (0.20 mmol) was added. After stirring for 15 min, benzosilacyclobutane (0.6 mmol) was added, and the reaction was continued to stir at 30 °C for 20 h. After monitoring the reaction by TLC until completion, sodium borohydride and methanol were directly added for reduction. Then, filtration, extraction were carried out, and the filtrate was concentrated and purified by silica gel column chromatography to obtain 52 mg of a pale yellow oily liquid product 3h with a yield of 75%.

[0086]

[0087] The physical and chemical indexes of this product are as follows: 1 HNMR(400MHz,CDCl3)δ7.56(d,J=8.0Hz,2H),7.17(d,J=8.0Hz,2H),7.10(d,J=7.5Hz,1H),7.02–6.95(m,1H),6.89–6.83(m,1H),6.48(dd,J=7.9,1.4Hz,1H),4.05(s,2H),2.15(s,2H),1.43(b,1H),0.16(s,5H). 19 F NMR(376MHz,CDCl3)δ-62.30.

[0088] 13 C NMR(101MHz,CDCl3)δ148.6,144.0,137.1,136.3,135.4,130.5,128.6,128.4,128.1(q,J=32.5Hz),126.3,124.4(q,J=3.7Hz),124.2,123.2(q,J=272.2Hz),62.7,20.3,-4.5.

[0089] HRMS(ESI)m / z:[M+Na] + calculated for C 19 H 19 NaF3OSi:371.1049,found:371.1049.

[0090] Example 9:

[0091] Under a nitrogen atmosphere, add the phosphine ligand L2 tris(4-methylphenyl)phosphine (6.1 mg, 0.02 mmol) and the metal catalyst bis(dibenzylideneacetone)palladium (5.7 mg, 0.01 mmol) to a Schlenk reaction tube. Then add 2.0 mL of toluene solvent. After pre-stirring at 30 °C for 10 min, add the phenylpropiolaldehyde compound 1i (0.20 mmol). After stirring for 15 min, add benzosilacyclobutane (0.6 mmol). Continue stirring the reaction at 30 °C for 20 h. After monitoring the reaction by TLC until it is complete, directly add sodium borohydride and methanol for reduction. Then filter, extract, concentrate the filtrate, and purify it by silica gel column chromatography to obtain 45 mg of a pale yellow oily liquid product 3i with a yield of 67%.

[0092]

[0093] The physical and chemical indexes of this product are as follows: 1 HNMR(400MHz,CDCl3)δ7.98(d,J=8.0Hz,2H),7.14(d,J=8.2Hz,2H),7.11–7.06(m,1H),7.01–6.95(m,1H),6.87–6.81(m,1H),6.49(dd,J=7.9,1.4Hz,1H),4.07(s,2H),3.85(s,3H),2.14(s,2H),1.65(b,1H),0.16(s,6H).

[0094] 13 C NMR(101MHz,CDCl3)δ166.0,148.9,145.3,136.9,136.4,135.4,130.4,128.7,128.6,128.2,127.6,126.2,124.2,62.7,51.2,20.4,-4.4.

[0095] HRMS(ESI)m / z:[M+Na] + calculated for C 20 H 22 NaO3Si:361.1230,found:361.1231.

[0096] Example 10:

[0097] Under a nitrogen atmosphere, the phosphine ligand L2 tris(4-methylphenyl)phosphine (6.1 mg, 0.02 mmol) and the metal catalyst bis(dibenzylideneacetone)palladium (5.7 mg, 0.01 mmol) were added to a Schlenk reaction tube. Then, 2.0 mL of diethyl ether solvent was added. After pre-stirring at 30 °C for 10 min, the propargyl aldehyde compound 1j (0.20 mmol) was added. After stirring for 15 min, benzosilacyclobutane (0.6 mmol) was added, and the reaction was continued to stir at 30 °C for 20 h. After monitoring the reaction by TLC and completion, sodium borohydride and methanol were directly added for reduction. Then, filtration, extraction were carried out, and the filtrate was concentrated and purified by silica gel column chromatography to obtain 45 mg of a pale yellow oily liquid product 3j with a yield of 77%.

[0098]

[0099] The physical and chemical indexes of this product: The mobile phase for flash chromatography: hexane / ethyl acetate = 10:1, colorless solid (45 mg, 77% yield, 13:1 rr, 14:1 cr), mp 94 - 96 °C. 1 H NMR (400 MHz, CDCl3) δ 7.23–7.16 (m, 1H), 7.09–7.03 (m, 2H), 6.99–6.94 (m, 1H), 6.89–6.82 (m, 3H), 6.64–6.59 (m, 1H), 4.09 (s, 2H), 2.27 (s, 3H), 2.13 (s, 2H), 1.41 (b, 1H), 0.15 (s, 6H).

[0100] 13 C NMR (101 MHz, CDCl3) δ 150.4, 140.0, 137.1, 137.0, 135.9, 135.3, 130.2, 128.9, 128.5, 127.2, 126.5, 126.0, 125.0, 124.1, 62.9, 20.5, -4.4.

[0101] HRMS (ESI) m / z: [M+Na] + calculated for C 19 H 22 NaOSi: 317.1332, found: 317.1329.

[0102] Example 11:

[0103] Under a nitrogen atmosphere, triphenylphosphine (6.1 mg, 0.02 mmol) and bis(dibenzylideneacetone)palladium (5.7 mg, 0.01 mmol) were added to a Schlenk reaction tube. Then, 2.0 mL of dichloroethane solvent was added. After pre-stirring at 30 °C for 10 min, propargyl aldehyde compound 1k (0.20 mmol) was added. After stirring for 15 min, benzosilacyclobutane (0.6 mmol) was added, and the reaction was continued to stir at 30 °C for 20 h. After monitoring the reaction by TLC until completion, sodium borohydride and methanol were directly added for reduction. Then, filtration, extraction were carried out, and the filtrate was concentrated and purified by silica gel column chromatography to obtain 43 mg of the product 3k as a pale yellow oily liquid with a yield of 69%.

[0104]

[0105] The physical and chemical indexes of this product are as follows: 1 H NMR (400 MHz, CDCl3) δ 7.22 (t, J = 7.9 Hz, 1H), 7.11–7.06 (m, 1H), 7.00–6.94 (m, 1H), 6.90–6.84 (m, 1H), 6.81–6.77 (m, 1H), 6.67–6.61 (m, 2H), 6.60–6.57 (m, 1H), 4.10 (s, 2H), 3.71 (s, 3H), 2.14 (s, 2H), 1.50 (b, 1H), 0.15 (s, 6H).

[0106] 13 C NMR (101 MHz, CDCl3) δ 158.7, 150.0, 141.5, 136.8, 136.1, 135.3, 130.3, 128.8, 128.4, 126.0, 124.1, 120.4, 113.4, 111.4, 62.8, 54.2, 20.4, -4.4.

[0107] HRMS (ESI) m / z: [M+Na] + calculated for C 19 H 22 NaO2Si: 333.1281, found: 333.1277.

[0108] Example 12:

[0109] Under a nitrogen atmosphere, add the phosphine ligand L2 tris(4-methylphenyl)phosphine (6.1 mg, 0.02 mmol) and the metal catalyst bis(dibenzylideneacetone)palladium (5.7 mg, 0.01 mmol) to a Schlenk reaction tube. Then add 2.0 mL of toluene solvent. After pre-stirring at 30 °C for 10 min, add the phenylpropiolaldehyde compound 1l (0.20 mmol). After stirring for 15 min, add benzosilacyclobutane (0.6 mmol). Continue stirring the reaction at 30 °C for 20 h. After monitoring the reaction by TLC and it is completed, directly add sodium borohydride and methanol for reduction. Then filter, extract, concentrate the filtrate, and purify by silica gel column chromatography to obtain 45 mg of a pale yellow oily liquid product 3l with a yield of 77%.

[0110]

[0111] The physical and chemical indexes of this product are as follows: 1 H NMR (400 MHz, CDCl3) δ 7.18–7.07 (m, 4H), 6.99–6.93 (m, 2H), 6.87–6.81 (m, 1H), 6.53 (dd, J = 7.9, 1.4 Hz, 1H), 4.03 (dd, J = 17.6, 12.4 Hz, 2H), 2.15 (s, 2H), 1.97 (s, 3H), 1.33 (b, 1H), 0.18 (s, 3H), 0.15 (s, 3H).

[0112] 13 C NMR (101 MHz, CDCl3) δ 149.0, 139.5, 136.4, 136.0, 135.3, 134.4, 130.4, 129.1, 128.0, 127.7, 126.1, 126.0, 124.9, 124.3, 63.1, 20.5, 18.3, -4.2, -4.4.

[0113] HRMS (ESI) m / z: [M+Na] + calculated for C 19 H 22 NaOSi: 317.1332, found: 317.1332.

[0114] Example 13:

[0115] Under a nitrogen atmosphere, add the phosphine ligand L2 tris(4-methylphenyl)phosphine (6.1 mg, 0.02 mmol) and the metal catalyst bis(dibenzylideneacetone)palladium (5.7 mg, 0.01 mmol) to a Schlenk reaction tube. Then add 2.0 mL of toluene solvent. After pre-stirring at 30 °C for 10 min, add the propargyl aldehyde compound 1m (0.20 mmol). After stirring for 15 min, add benzosilacyclobutane (0.6 mmol). Continue stirring the reaction at 30 °C for 20 h. After monitoring the reaction by TLC and it is completed, directly add sodium borohydride and methanol for reduction. Then filter, extract, concentrate the filtrate, and purify by silica gel column chromatography to obtain 53 mg of the pale yellow oily liquid product 3m with a yield of 85%.

[0116]

[0117] The physical and chemical indexes of this product are as follows: 1 H NMR(400MHz,CDCl3)δ7.28–7.22(m,1H),7.12–7.06(m,1H),7.01–6.83(m,5H),6.54(dd,J=7.9,1.4Hz,1H),3.98(dd,J=33.2,11.2Hz,2H),3.67(s,3H),2.13(dd,J=37.6,15.2Hz,2H),1.74(b,1H),0.20(s,3H),0.12(s,3H).

[0118] 13 C NMR(101MHz,CDCl3)δ155.4,146.4,136.9,136.7,135.5,130.2,129.7,129.0,128.1,127.5,125.9,124.2,120.2,110.3,63.0,54.9,20.3,-4.4,-4.8.

[0119] HRMS(ESI)m / z:[M+Na] + calculated for C 19 H 22 NaO2Si:333.1281,found:333.1278.

[0120] Example 14:

[0121] Under a nitrogen atmosphere, the phosphine ligand L2 tris(4-methylphenyl)phosphine (6.1 mg, 0.02 mmol) and the metal catalyst bis(dibenzylideneacetone)palladium (5.7 mg, 0.01 mmol) were added to a Schlenk reaction tube. Then, 2.0 mL of toluene solvent was added. After pre-stirring at 30 °C for 10 min, the propargyl aldehyde compound 1n (0.20 mmol) was added. After stirring for 15 min, benzosilacyclobutane (0.6 mmol) was added, and the reaction was continued to stir at 30 °C for 20 h. After monitoring the reaction by TLC and it was completed, sodium borohydride and methanol were directly added for reduction. Then, it was filtered, extracted, the filtrate was concentrated, and purified by silica gel column chromatography to obtain 57 mg of a pale yellow oily liquid product 3n with a yield of 80%.

[0122]

[0123] The physical and chemical indexes of this product are as follows: 1 H NMR (400 MHz, CDCl3) δ 7.62 (dd, J = 7.7, 1.5 Hz, 1H), 7.57–7.45 (m, 4H), 7.41–7.36 (m, 3H), 7.29 (d, J = 7.4 Hz, 1H), 7.25–7.13 (m, 3H), 7.02 (dd, J = 7.8, 1.5 Hz, 1H), 4.03 (dd, J = 39.2, 12.4 Hz, 2H), 2.23 (dd, J = 88.4, 15.6 Hz, 2H), 0.30 (s, 3H), 0.20 (s, 3H).

[0124] 13 C NMR (101 MHz, CDCl3) δ 147.1, 140.1, 139.5, 138.7, 138.0, 136.2, 136.0, 130.3, 129.2, 129.1, 128.5, 127.8, 127.0, 126.6, 126.5, 126.2, 126.0, 124.2, 63.3, 20.4, -5.1, -5.3.

[0125] HRMS (ESI) m / z: [M+Na] + calculated for C 24 H 24 NaOSi: 379.1489, found: 379.1486.

[0126] Example 15:

[0127] Under a nitrogen atmosphere, add the phosphine ligand L2 tris(4-methylphenyl)phosphine (6.1 mg, 0.02 mmol) and the metal catalyst bis(dibenzylideneacetone)palladium (5.7 mg, 0.01 mmol) to a Schlenk reaction tube. Then add 2.0 mL of toluene solvent. After pre-stirring at 30 °C for 10 min, add the phenylpropiolaldehyde compound 1o (0.20 mmol). After stirring for 15 min, add benzosilacyclobutane (0.6 mmol). Continue stirring the reaction at 30 °C for 20 h. After monitoring the reaction by TLC until it is completed, directly add sodium borohydride and methanol for reduction. Then filter, extract, concentrate the filtrate, and purify it by silica gel column chromatography to obtain 45 mg of a pale yellow oily liquid product 3o with a yield of 73%.

[0128]

[0129] The physical and chemical indicators of this product are as follows: 1 H NMR (400 MHz, CDCl3) δ 7.07 (dd, J = 7.4, 1.4 Hz, 1H), 6.99–6.93 (m, 1H), 6.90–6.83 (m, 2H), 6.69–6.62 (m, 3H), 4.10 (s, 2H), 2.23 (s, 6H), 2.13 (s, 2H), 1.42 (b, 1H), 0.14 (s, 6H).

[0130] 13 C NMR (101 MHz, CDCl3) δ 150.5, 140.0, 137.1, 136.8, 135.6, 135.3, 130.2, 128.9, 127.3, 125.9, 125.6, 124.0, 62.9, 20.5, 20.3, -4.4.

[0131] HRMS (ESI) m / z: [M+Na] + calculated for C 20 H 24 NaOSi: 331.1489, found: 331.1486.

[0132] Example 16:

[0133] Under a nitrogen atmosphere, add the phosphine ligand L2 tris(4-methylphenyl)phosphine (6.1 mg, 0.02 mmol) and the metal catalyst bis(dibenzylideneacetone)palladium (5.7 mg, 0.01 mmol) to a Schlenk reaction tube. Then add 2.0 mL of n-hexane and dichloromethane solvents. After pre-stirring at 30 °C for 10 min, add the phenylpropiolaldehyde compound 1p (0.20 mmol). After stirring for 15 min, add benzosilacyclobutane (0.6 mmol). Continue stirring the reaction at 30 °C for 20 h. After monitoring the reaction by TLC and it is completed, directly add sodium borohydride and methanol for reduction. Then filter, extract, concentrate the filtrate, and purify it by silica gel column chromatography to obtain 45 mg of a pale yellow oily liquid product 3p with a yield of 71%.

[0134]

[0135] The physical and chemical indexes of this product are as follows: 1 H NMR(400MHz,CDCl3)δ7.10(d,J=7.5Hz,1H),7.01(t,J=7.4Hz,1H),6.90(t,J=7.6Hz,1H),6.75–6.67(m,1H),6.66–6.54(m,3H),4.11(s,2H),2.13(s,2H),1.52(b,1H),0.16(s,6H).

[0136] 19 F NMR(376MHz,CDCl3)δ-109.64.

[0137] 13 C NMR(101MHz,CDCl3)δ162.2(d,J=249.9Hz),160.0(d,J=249.8Hz),143.5,143.5(d,J=18.0Hz),137.3,135.8,135.3,130.5,128.4,126.4,124.3,111.1(d,J=24.9Hz),111.1(d,J=11.4Hz),101.4(t,J=25.1Hz),62.7,20.3,-4.5.HRMS(ESI)m / z:[M+Na] + calculated for C 18 H 18 NaF2OSi:339.0987,found:339.0984.

[0138] Example 17:

[0139] Under a nitrogen atmosphere, the phosphine ligand L2 tris(4-methylphenyl)phosphine (6.1 mg, 0.02 mmol) and the metal catalyst bis(dibenzylideneacetone)palladium (5.7 mg, 0.01 mmol) were added to a Schlenk reaction tube. Then, 2.0 mL of n-hexane and dichloromethane solvents were added. After pre-stirring at 30 °C for 20 min, the propargyl aldehyde compound 1q (0.20 mmol) was added. After stirring for 15 min, benzosilacyclobutane (0.6 mmol) was added, and the reaction was continued to stir at 30 °C for 20 h. After monitoring the reaction by TLC and completion of the reaction, sodium borohydride and methanol were directly added for reduction. Then, filtration, extraction were carried out, and the filtrate was concentrated and purified by silica gel column chromatography to obtain 45 mg of a pale yellow oily liquid product 3q with a yield of 68%.

[0140]

[0141] The physical and chemical indexes of this product are as follows: 1 HNMR(400MHz,CDCl3)δ7.81–7.69(m,3H),7.54(s,1H),7.45–7.36(m,2H),7.18–7.07(m,2H),7.00–6.94(m,1H),6.83–6.77(m,1H),6.59(dd,J=7.9,1.4Hz,1H),4.12(s,2H),2.17(s,2H),1.39(b,1H),0.17(s,6H). 13 C NMR(101MHz,CDCl3)δ150.0,137.6,137.0,136.6,135.4,132.3,131.2,130.3,129.0,127.0,126.9,126.7,126.6,126.4,126.1,125.2,124.8,124.1,62.9,20.4,-4.4.HRMS(ESI)m / z:[M+Na] + calculated for C 22 H 22 NaOSi:353.1332,found:353.1335.

[0142] Example 18:

[0143] Under a nitrogen atmosphere, add the phosphine ligand L3 tricyclohexylphosphine tetrafluoroborate (7.4 mg, 0.02 mmol) and the metal catalyst bis(dibenzylideneacetone)palladium (5.7 mg, 0.01 mmol) to a Schlenk reaction tube. Then add 2.0 mL of n-hexane and dichloroethane solvents. After pre-stirring at 30 °C for 10 min, add the phenylpropiolaldehyde compound 1a (0.20 mmol). After stirring for 15 min, add benzosilacyclobutane (0.6 mmol). Continue stirring the reaction at 30 °C for 20 h. After monitoring the reaction by TLC until it is completed, directly add sodium borohydride and methanol for reduction. Then filter, extract, concentrate the filtrate, and purify it by silica gel column chromatography to obtain 35 mg of a pale yellow oily liquid product 4a with a yield of 63%. Its 1H NMR spectrum is as shown in Figure 5 shown, and its 13C NMR spectrum is as shown in Figure 6 shown.

[0144]

[0145] The physical and chemical indexes of this product are as follows: 1 1H NMR (400 MHz, CDCl3) δ 7.61–7.54 (m, 1H), 7.28 (t, J = 7.5 Hz, 2H), 7.19–7.06 (m, 4H), 6.99–6.92 (m, 2H), 4.39 (s, 2H), 2.14 (s, 2H), 1.48 (b, 1H), -0.08 (s, 6H).

[0146] 13 13C NMR (101 MHz, CDCl3) δ 145.3, 143.0, 141.0, 135.6, 134.5, 130.8, 127.5, 126.3, 126.0, 125.7, 124.9, 124.7, 59.9, 20.1, -5.4.

[0147] HRMS (ESI) m / z: [M+Na] + calculated for C 18 H 20 NaOSi: 303.1176, found: 303.1176.

[0148] Example 19:

[0149] Under a nitrogen atmosphere, the phosphine ligand tricyclohexylphosphine tetrafluoroborate (3.7 mg, 0.01 mmol) and the metal catalyst bis(dibenzylideneacetone)palladium (5.7 mg, 0.01 mmol) were added to a Schlenk reaction tube. Then, 2.0 mL of toluene solvent was added. After pre-stirring at 30 °C for 10 min, the phenylpropiolaldehyde compound 1b (0.20 mmol) was added. After stirring for 15 min, benzosilacyclobutane (0.4 mmol) was added, and the reaction was continued to stir at 30 °C for 12 h. After monitoring the reaction by TLC and completion, sodium borohydride and methanol were directly added for reduction, then filtered, extracted, the filtrate was concentrated, and purified by silica gel column chromatography to obtain 25 mg of a pale yellow oily liquid product 4b with a yield of 43%.

[0150]

[0151] The physical and chemical indexes of this product are as follows: 1 H NMR (400 MHz, CDCl3) δ 7.56 (d, J = 7.7 Hz, 1H), 7.16–7.03 (m, 5H), 6.84 (d, J = 7.9 Hz, 2H), 4.38 (s, 2H), 2.29 (s, 3H), 2.12 (s, 2H), 1.51 (b, 1H), -0.09 (s, 6H).

[0152] 13 C NMR (101 MHz, CDCl3) δ 145.4, 143.0, 137.9, 135.5, 134.6, 134.2, 130.7, 128.2, 126.2, 126.0, 125.6, 124.8, 59.9, 20.1, -5.4.

[0153] HRMS (ESI) m / z: [M+K] + calculated for C 19 H 22 KOSi: 333.1072, found: 333.1068.

[0154] Example 20:

[0155] Under a nitrogen atmosphere, add the phosphine ligand L3 tricyclohexylphosphine tetrafluoroborate (3.7 mg, 0.01 mmol) and the metal catalyst bis(dibenzylideneacetone)palladium (5.7 mg, 0.01 mmol) to a Schlenk reaction tube. Then add 2.0 mL of n-hexane and dichloroethane solvents. After pre-stirring at 30 °C for 20 min, add the phenylpropiolaldehyde compound 1c (0.20 mmol). After stirring for 15 min, add benzosilacyclobutane (0.6 mmol). Continue stirring the reaction at 30 °C for 24 h. After monitoring the reaction by TLC and it is completed, directly add sodium borohydride and methanol for reduction. Then filter, extract, concentrate the filtrate, and purify it by silica gel column chromatography to obtain 35 mg of a pale yellow oily liquid product 4c with a yield of 63%.

[0156]

[0157] The physical and chemical indexes of this product are as follows: 1 H NMR (400 MHz, CDCl3) δ 7.55 (d, J = 8.2 Hz, 1H), 7.18–7.04 (m, 34H), 6.91–6.79 (m, 4H), 4.39 (s, 2H), 3.75 (s, 3H), 2.12 (s, 2H), 1.57 (b, 1H), -0.09 (s, 6H).

[0158] 13 C NMR (101 MHz, CDCl3) δ 156.7, 145.7, 142.6, 135.6, 134.6, 133.1, 130.7, 127.2, 126.2, 125.6, 124.8, 112.9, 59.8, 54.2, 20.1, -5.4.

[0159] HRMS (ESI) m / z: [M+Na] + calculated for C 19 H 22 NaO2Si: 333.1281, found: 333.1275.

[0160] Example 21:

[0161] Under a nitrogen atmosphere, add tricyclohexylphosphine tetrafluoroborate (7.4 mg, 0.02 mmol) of phosphine ligand L3 and bis(dibenzylideneacetone)palladium (5.7 mg, 0.01 mmol) of metal catalyst to a Schlenk reaction tube, then add 2.0 mL of toluene solvent. After pre-stirring at 30 °C for 10 min, add propargyl aldehyde compound 1d (0.20 mmol). After stirring for 15 min, add benzosilacyclobutane (0.4 mmol). Continue stirring the reaction at 30 °C for 20 h. After monitoring the reaction by TLC and it is completed, directly add sodium borohydride and methanol for reduction, then filter, extract, concentrate the filtrate, and purify by silica gel column chromatography to obtain 35 mg of a pale yellow oily liquid product 4d with a yield of 59%.

[0162]

[0163] The physical and chemical indexes of this product are as follows: 1 H NMR (400 MHz, CDCl3) δ 7.54 (d, J = 8.2 Hz, 1H), 7.18–7.03 (m, 3H), 7.03–6.93 (m, 2H), 6.95–6.87 (m, 2H), 4.37 (s, 2H), 2.13 (s, 2H), 1.55 (b, 1H), -0.09 (s, 6H).

[0164] 19 F NMR (376 MHz, CDCl3) δ -117.34.

[0165] 13 C NMR (101 MHz, CDCl3) δ 160.2 (d, J = 244.3 Hz), 145.9, 141.9, 136.7 (d, J = 3.5 Hz), 135.5, 134.2, 130.8, 127.6 (d, J = 7.7 Hz), 126.4, 125.6, 124.9, 114.4 (d, J = 21.1 Hz), 59.7, 20.0, -5.5.

[0166] HRMS (ESI) m / z: [M+Na] + calculated for C 18 H 19 NaFOSi: 321.1081, found: 321.1076.

[0167] Example 22:

[0168] Under a nitrogen atmosphere, add the phosphine ligand L3 tricyclohexylphosphine tetrafluoroborate (7.4 mg, 0.02 mmol) and the metal catalyst bis(dibenzylideneacetone)palladium (5.7 mg, 0.01 mmol) to a Schlenk reaction tube. Then add 2.0 mL of toluene solvent. After pre-stirring at 30 °C for 10 min, add the phenylpropiolaldehyde compound 1n (0.20 mmol). After stirring for 15 min, add benzosilacyclobutane (0.6 mmol). Continue stirring the reaction at 30 °C for 20 h. After monitoring the reaction by TLC and it is completed, directly add sodium borohydride and methanol for reduction. Then filter, extract, concentrate the filtrate, and purify it by silica gel column chromatography to obtain 37 mg of a pale yellow oily liquid product 4e with a yield of 52%.

[0169]

[0170] The physical and chemical indexes of this product are as follows: 1 H NMR(400MHz,CDCl3)δ7.59–7.49(m,5H),7.40–7.33(m,2H),7.29–7.23(m,1H),7.17–7.11(m,2H),7.10–7.00(m,3H),4.42(s,2H),2.14(s,2H),1.54(b,1H),-0.06(s,6H).

[0171] 13 C NMR(101MHz,CDCl3)δ145.5,142.6,140.1,139.7,137.5,135.6,134.4,130.8,127.8,126.6,126.3,126.1,125.9,125.7,124.9,59.9,20.1,-5.3.

[0172] HRMS(ESI)m / z:[M+Na] + calculated for C 24 H 24 NaOSi:379.1489,found:379.1485.

[0173] Example 23:

[0174] Under a nitrogen atmosphere, phosphine ligand tricyclohexylphosphine tetrafluoroborate (7.4 mg, 0.02 mmol) and metal catalyst bis(dibenzylideneacetone)palladium (5.7 mg, 0.01 mmol) were added to a Schlenk reaction tube. Then, 2.0 mL of toluene solvent was added. After pre-stirring at 30 °C for 10 min, propargyl aldehyde compound 1i (0.20 mmol) was added. After stirring for 15 min, benzosilacyclobutane (0.6 mmol) was added, and the reaction was continued to stir at 30 °C for 20 h. After monitoring the reaction by TLC until completion, sodium borohydride and methanol were directly added for reduction. Then, filtration, extraction were carried out, and the filtrate was concentrated and purified by silica gel column chromatography to obtain 36 mg of a pale yellow oily liquid product 4f with a yield of 53%.

[0175]

[0176] The physical and chemical indexes of this product are as follows: 1 HNMR(400MHz,CDCl3)δ7.96(d,J=8.3Hz,2H),7.56(d,J=8.2Hz,1H),7.17–7.06(m,3H),7.04(d,J=8.3Hz,2H),4.35(s,2H),3.85(s,3H),2.14(s,2H),1.65(b,1H),-0.10(s,6H).

[0177] 13 C NMR(101MHz,CDCl3)δ166.1,146.6,145.4,142.0,135.5,134.0,130.8,128.9,126.6,126.6,126.2,125.8,124.9,59.8,51.1,19.9,-5.5.

[0178] HRMS(ESI)m / z:[M+Na] + calculated for C 20 H 22 NaO3Si:361.1230,found:361.1229.

[0179] Example 24:

[0180] Under a nitrogen atmosphere, add the phosphine ligand L3 tricyclohexylphosphine tetrafluoroborate (7.4 mg, 0.02 mmol) and the metal catalyst bis(dibenzylideneacetone)palladium (5.7 mg, 0.01 mmol) to a Schlenk reaction tube. Then add 2.0 mL of toluene solvent. After pre-stirring at 30 °C for 10 min, add the phenylpropiolaldehyde compound 1j (0.20 mmol). After stirring for 15 min, add benzosilacyclobutane (0.6 mmol). Continue stirring the reaction at 30 °C for 20 h. After monitoring the reaction by TLC and it is completed, directly add sodium borohydride and methanol for reduction. Then filter, extract, concentrate the filtrate, and purify by silica gel column chromatography to obtain 26 mg of a pale yellow oily liquid product 4g with a yield of 44%.

[0181]

[0182] The physical and chemical indexes of this product are as follows: 1 H NMR (400 MHz, CDCl3) δ 7.56 (d, J = 7.7 Hz, 1H), 7.19–7.11 (m, 3H), 7.10–7.05 (m, 1H), 6.97 (d, J = 7.6 Hz, 1H), 6.78–6.72 (m, 2H), 4.38 (s, 2H), 2.29 (s, 3H), 2.13 (s, 2H), 1.51 (b, 1H), -0.09 (s, 6H).

[0183] 13 C NMR (101 MHz, CDCl3) δ 145.2, 143.1, 140.9, 137.1, 135.5, 134.6, 130.7, 127.4, 126.6, 126.2, 125.6, 125.5, 124.8, 123.1, 59.9, 20.6, 20.1, -5.4.

[0184] HRMS (ESI) m / z: [M+Na] + calculated for C 19 H 22 NaOSi: 317.1332, found: 137.1332.

[0185] Example 25:

[0186] Under a nitrogen atmosphere, phosphine ligand L3 tricyclohexylphosphine tetrafluoroborate (7.4 mg, 0.02 mmol) and metal catalyst bis(dibenzylideneacetone)palladium (5.7 mg, 0.01 mmol) were added to a Schlenk reaction tube. Then, 2.0 mL of toluene solvent was added. After pre-stirring at 30 °C for 10 min, propargyl aldehyde compound 1k (0.20 mmol) was added. After stirring for 15 min, benzosilacyclobutane (0.6 mmol) was added, and the reaction was continued to stir at 30 °C for 20 h. After monitoring the reaction by TLC until completion, sodium borohydride and methanol were directly added for reduction. Then, filtration, extraction were carried out, and the filtrate was concentrated and purified by silica gel column chromatography to obtain 33 mg of a pale yellow oily liquid product 4h with a yield of 53%.

[0187]

[0188] The physical and chemical indexes of this product are as follows: 1 H NMR (400 MHz, CDCl3) δ 7.60–7.54 (m, 1H), 7.23–7.07 (m, 5H), 6.74–6.68 (m, 1H), 6.55–6.46 (m, 2H), 4.39 (s, 2H), 3.74 (s, 3H), 2.13 (s, 2H), 1.55 (b, 1H), -0.08 (s, 6H).

[0189] 13 C NMR (101 MHz, CDCl3) δ 158.6, 145.3, 142.8, 142.5, 135.5, 134.4, 130.7, 128.6, 126.3, 125.7, 124.8, 118.5, 111.7, 109.9, 60.0, 54.1, 20.1, -5.4.

[0190] HRMS (ESI) m / z: [M+Na] + calculated for C 19 H 22 NaO2Si: 333.1281, found: 333.1277.

[0191] Example 26:

[0192] Under a nitrogen atmosphere, add the phosphine ligand L3 tricyclohexylphosphine tetrafluoroborate (7.4 mg, 0.02 mmol) and the metal catalyst bis(dibenzylideneacetone)palladium (5.7 mg, 0.01 mmol) into a Schlenk reaction tube. Then add 2.0 mL of toluene solvent. After pre-stirring at 30 °C for 10 min, add the phenylpropiolaldehyde compound 1q (0.20 mmol). After stirring for 15 min, add benzosilacyclobutane (0.6 mmol). Continue stirring the reaction at 30 °C for 20 h. After monitoring the reaction by TLC until it is completed, directly add sodium borohydride and methanol for reduction. Then filter, extract, concentrate the filtrate, and purify it by silica gel column chromatography to obtain 26 mg of a pale yellow oily liquid product 4i with a yield of 39%.

[0193]

[0194] The physical and chemical indexes of this product are as follows: 1 H NMR(400MHz,CDCl3)δ7.79–7.71(m,3H),7.58(d,J=7.8Hz,1H),7.44–7.35(m,3H),7.18–7.07(m,4H),4.40(s,2H),2.17(s,2H),1.59(b,1H),-0.07(s,6H).

[0195] 13 C NMR(101MHz,CDCl3)δ145.7,142.9,138.7,135.6,134.5,132.5,130.8,130.7,127.2,126.7,126.6,126.4,125.7,125.3,125.2,124.9,124.4,123.8,60.0,20.1,-5.4.HRMS(ESI)m / z:[M+Na] + calculated for C 22 H 22 NaOSi:353.1332,found:353.1326.

[0196] In summary, the above are only the preferred embodiments of the present invention. All equivalent changes and modifications made according to the scope of the patent application of the present invention shall fall within the scope covered by the patent of the present invention.

Claims

1. A 1,2-dihydrobenzodisilacyclohexane compound, characterized in that, The compound has a structural formula shown in the following formula (I) or formula (II): In the formula, R1 is one of hydrogen, alkyl, halogenated group, alkoxy group or phenyl group.

2. A method for preparing a 1,2-dihydrobenzodisilacyclohexane compound as described in claim 1, characterized in that, The preparation method includes the following steps: Under an inert gas atmosphere, a phosphine ligand, a palladium metal catalyst, an additive and a reaction medium are mixed, and after stirring for 10 - 20 min, a propargyl aldehyde compound 1 and a benzosilacyclobutane 2 are added in sequence. After the reaction, sodium borohydride is added for reduction. After removing the solvent, the 1,2-dihydrobenzosilacyclohexane compound is obtained by separation and purification.

3. The preparation method according to claim 2, characterized in that, The molar ratio of the propargyl aldehyde compound to the benzosilacyclobutane is 1:2 to 1:

3.

4. The preparation method according to claim 2, wherein The palladium metal catalyst is bis(dibenzylideneacetone)palladium(0).

5. The preparation method according to claim 4, characterized in that, The usage amount of the palladium metal catalyst is 3 - 6% of the molar amount of the propargyl aldehyde compound.

6. The preparation method according to claim 2, characterized in that, The phosphine ligand is selected from one of triphenylphosphine, tris(4-methylphenyl)phosphine or tricyclohexylphosphine tetrafluoroborate.

7. The preparation method according to claim 6, characterized in that The usage amount of the phosphine ligand is 10 - 12% of the molar amount of the propargyl aldehyde compound.

8. The preparation method according to claim 2, wherein The reaction medium is selected from one of n-hexane, toluene, dichloromethane, dichloroethane, diethyl ether or a mixture of two of them.

9. The preparation method according to claim 2, characterized in that, The reaction temperature is 10 - 40 °C, and the reaction time is 10 - 24 h.

10. Use of the 1,2-dihydrobenzosilacyclohexane compound according to claim 1 as a luminescent material or as a precursor for drug synthesis.

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