Functionalized plane chiral pillararene as well as preparation method and application thereof

Abstract

The invention discloses a functionalized planar chiral pillararene and a preparation method and application thereof, the functionalized planar chiral pillararene comprises a compound I, a compound II, a compound III, a compound IV, a compound V and a compound VI, and also comprises stereoisomers of the compound I, the compound II, the compound III, the compound IV, the compound V or the compound VI; the preparation method comprises the following steps: adding an organic boron compound, a palladium catalyst, a chiral ligand, alkali and column [n] arene into a solvent according to a certain proportion, carrying out an anaerobic heating reaction, and after the reaction is finished, carrying out post-treatment to obtain the chiral column arene derivative. When n is equal to 5, the column [n] arene is a compound VII, and when n is equal to 6, the column [n] arene is a compound VIII. According to the functionalized surface chiral pillararene and the preparation method and application thereof, the chiral pillararene derivative with high yield, high ee value, high optical activity, excellent fluorescence emission performance and large electron-rich cavity is obtained, and the chiral pillararene derivative can be used as a chiral luminescent material, a chiral catalyst carrier and the like.

Description

Technical Field

[0001] The invention relates to the technical field of chiral pillar aromatic hydrocarbon supramolecular materials, and in particular to a functionalized planar chiral pillar aromatic hydrocarbon and a preparation method and application thereof. Background Art

[0002] The property of chirality exists in various fields such as organisms, materials, and drugs, and plays a vital role in life. It is the basic substance involved in the formation of life in nature, such as nucleotides, amino acids, and monosaccharides, as well as the biological macromolecules nucleic acids, proteins, and sugars composed of them. Many physical, chemical, and biological functions originate from the precise recognition and strict matching of molecular chirality, such as the high stereoselectivity of enzyme catalysis and the different biological responses of different conformations of chiral drugs.

[0003] Due to their unique cavity structure, macrocyclic compounds can selectively identify and assemble with a variety of compounds through host-guest interactions, so macrocyclic compounds can be used as catalyst carriers, controlled synthesis of nanotubes, phase transfer catalysts, etc. Introducing chirality into macrocyclic compounds or controlling the chirality of macrocyclic compounds will give macrocyclic compounds better properties and broad application prospects, such as constructing chiral luminescent materials, chiral catalyst carriers, chiral nanotubes, and selectively identifying and assembling chiral guest molecules with chiral macrocyclic molecules as primitives.

[0004] Pillarene molecules are a new generation of macrocyclic host molecules first synthesized and reported by Ogoshi in 2008. Pillarene molecules are not only simple to synthesize, but also have unique columnar structures, electron-rich cavities and multiple modification sites, which allow them to selectively complex guest molecules and are easy to functionalize, making their properties highly tunable. They have shown potential application prospects in many fields, thus arousing great research interest.

[0005] Pillar aromatic molecules lack symmetry planes, and even if all alkoxy or hydroxyl groups are the same, they do not have symmetry and show inherent chirality, thus producing a pair of enantiomers. When the alkoxy groups connected to the upper and lower edges of pillar aromatics are small, the pillar aromatic molecules at room temperature show rheological conformation as the aromatic ring fragments flip. In order to control the conformational flip of pillar aromatics, the pillar aromatics must be modified by introducing rigid fragments or large steric groups on the upper and lower edges of pillar aromatics to increase the energy barrier to overcome the flip, inhibit its flip, and obtain a stable conformation.

[0006] In the prior art, optically pure intrinsic chiral columnar aromatics molecules are mainly obtained by chiral high performance liquid chromatography separation. This method is time-consuming and labor-intensive, and the separation amount is mostly in the milligram level. There are defects such as high difficulty in the synthesis and separation of chiral columnar aromatics and limited preparation scale, which greatly restricts the application research of chiral columnar aromatics. Summary of the invention

[0007] The purpose of the present invention is to provide a functionalized face chiral pillar aromatic hydrocarbon and its preparation method and application, so as to prepare a series of stable face chiral pillar aromatic hydrocarbon derivatives with high yield, high ee value, high optical activity, excellent fluorescence emission performance and large electron-rich cavity, which can be used as chiral luminescent materials, chiral catalyst carriers, etc.

[0008] To achieve the above-mentioned object, the present invention provides a functionalized planar chiral pillar aromatic hydrocarbon, including compound I, compound II, compound III, compound IV, compound V and compound VI, and also includes stereoisomers of the compound I, the compound II, the compound III, the compound IV, the compound V or the compound VI;

[0009] The structural formulas of the compound I, the compound II, the compound III, the compound IV, the compound V and the compound VI are respectively as follows:

[0010]

[0011] Among them, R 1 Selected from C 1-10 Alkyl, C 3-10 Cycloalkyl, C 5-15 Aryl, benzyl, the C 1-10 The alkyl group is optionally inserted by one or more groups selected from oxygen atoms, carbonyl groups, and the C 3-10 Cycloalkyl, the C 5-15 The aryl group and the benzyl group are each independently optionally substituted with one or more C 1-5 Alkyl substitution;

[0012] R 2 and R 3 Different and each independently selected from C 5-15 Aryl, C 5-15 Heteroaryl, the R 2 Optionally one or more independently selected from R a Substituents, said R 3 Optionally one or more independently selected from R m substituted by a substituent;

[0013] Among them, the R a , the R m Each independently selected from C 1-10 Alkyl, C 1-10 Alkoxy, C 5-15 Aryloxy, C 6-16 Arylalkoxy, C 2-10 Alkenyl, C 2-10 Alkynyl, C 3-10Cycloalkyl, C 5-15 Aryl, C 5-15 heteroaryl, halogen, trifluoromethyl, nitro, cyano, the R a Optionally one or more independently selected from R b Substituents, said R m Optionally one or more independently selected from R n Substituents are substituted;

[0014] Among them, the R b , the R n Each independently selected from C 1-10 Alkyl, C 1-10 Alkoxy, C 2-10 Alkenyl, C 2-10 Alkynyl, C 3-10 Cycloalkyl, C 5-15 Aryl, C 5-15 Heteroaryl, halogen, trifluoromethyl, nitro, cyano.

[0015] Preferably, the R 1 Selected from methyl, ethyl, propyl, butyl, 3-carbomethyl, cyclohexyl, benzyl, naphthylmethyl, anthracenemethyl and phenanthrylmethyl.

[0016] Preferably, the R 2 , the R 3 Each is independently selected from phenyl, naphthyl, anthracenyl, phenanthrenyl, pyrenyl;

[0017] The R a , R m Each is independently selected from methyl, methoxy, ethyl, propyl, butyl, tert-butyl, phenyl, benzyloxy, fluoro, cyano, nitro, trifluoromethyl.

[0018] Preferably, the R 2 , the R 3 Each is independently selected from p-methoxyphenyl, p-ethoxyphenyl, p-methylphenyl, p-ethylphenyl, p-propylphenyl, p-tert-butylphenyl, p-benzylphenyl, p-nitrophenyl, p-fluorophenyl, p-trifluoromethylphenyl, p-cyanophenyl, p-nitrophenyl, naphthyl, anthracenyl, phenanthrenyl, pyrenyl and tetraphenylethylene.

[0019] To achieve the above object, the present invention also provides a method for preparing functionalized planar chiral pillar aromatics, comprising the following steps:

[0020] According to a certain ratio, an organic boron compound, a palladium catalyst, a chiral ligand, a base and pillar[n]arene are added to a solvent for an oxygen-free heating reaction, and after the reaction is completed, a post-treatment is performed to obtain a chiral pillar[n]arene derivative;

[0021] Wherein, when n=5, the pillar[n]arene is compound VII, and its structural formula is as follows:

[0022]

[0023] When n=6, the pillar[n]arene is compound VIII, and its structural formula is as follows:

[0024]

[0025] Among them, R 1 Selected from C 1-10 Alkyl, C 3-10 Cycloalkyl, C 5-15 Aryl, benzyl, the C 1-10 The alkyl group is optionally inserted by one or more groups selected from oxygen atoms, carbonyl groups, and the C 3-10 Cycloalkyl, the C 5-15 The aryl group and the benzyl group are each independently optionally substituted with one or more C 1-5 Alkyl substitution.

[0026] Preferably, the organic boronic acid compound is one of 4-methoxyphenylboric acid, 4-methylphenylboric acid, 4-ethylphenylboric acid, 4-propylphenylboric acid, 4-tert-butylphenylboric acid, 4-fluorophenylboric acid, 4-nitrobenzeneboric acid, 4-trifluoromethylphenylboric acid, 4-cyanophenylboric acid, 4-phenylphenylboric acid, 4-benzyloxyphenylboric acid, naphthylphenylboric acid, anthracenylphenylboric acid, phenanthrenylphenylboric acid, pyrenylphenylboric acid, 9,10-diphenylanthrylboric acid, p-triphenylvinylphenylboric acid, and p-terpyridylphenylboric acid;

[0027] The molar ratio of the pillar[n]arene to the organic boronic acid compound is greater than 1:2.

[0028] Preferably, the palladium catalyst comprises an organic palladium catalyst, and the organic palladium catalyst is one or more of Pd(PPh3)4, Pd2(dba)3, and Pd(OAc)2;

[0029] The chiral ligand includes a chiral phosphimide ligand;

[0030] The base is one or more of alkali metal phosphates, alkali metal carbonates, alkali metal acetates, organic amines, and alkali metal alkylsilanols;

[0031] The solvent is an organic solvent or an aqueous solution of an organic solvent.

[0032] Preferably, the palladium catalyst is Pd(OAc)2;

[0033] The chiral phosphimide ligand is L22 or one of the stereoisomers of L22, the L22 is in R form, the stereoisomer of L22 is in S form, and the structural formula of L22 is as follows:

[0034]

[0035] The alkali is one or both of Na3PO4 and K3PO4.

[0036] Preferably, the organic solvent is one or more of toluene, 1,4-dioxane, N,N-dimethylformamide, N,N-dimethylacetamide, and tetrahydrofuran, and the volume ratio of the organic solvent to water in the aqueous solution of the organic solvent is greater than 4.

[0037] To achieve the above-mentioned purpose, the present invention also provides an application of a functionalized planar chiral pillar aromatic hydrocarbon in a chiral luminescent material and a chiral catalyst carrier.

[0038] Therefore, the present invention adopts the above-mentioned functionalized planar chiral pillar aromatic hydrocarbon and its preparation method and application, and the beneficial effects are as follows:

[0039] (1) The present invention utilizes asymmetric catalytic Suzuki coupling reaction to introduce large steric rigid fragment modification, inhibits the flipping of column [n] aromatics (n = 5, 6), and prepares optically pure chiral column [n] aromatics (n = 5, 6) of a single conformation. Large steric rigid fragment modified column [n] aromatics (n = 5, 6) have excellent fluorescence emission properties, are a combination of supramolecules and chirality, and are a very important class of chiral luminescent materials. Since the obtained compounds have optical activity, fluorescence emission, and a large electron-rich cavity, they have broad application prospects in chiral luminescent materials, chiral catalyst carriers, and the like.

[0040] (2) The present invention provides a method for synthesizing chiral column [n] aromatic hydrocarbons (n ​​= 5, 6), which uses a transition metal-catalyzed asymmetric Suzuki coupling reaction under a nitrogen atmosphere to introduce large sterically hindered rigid fragments such as phenyl, substituted phenyl, benzyl, pyrene, biphenyl, anthracene, etc., with very high optical purity (ee values ​​are all greater than 95%) to obtain optically active column [n] aromatic hydrocarbons (n ​​= 5, 6).

[0041] (3) The present invention provides a method for synthesizing chiral columnar [n] aromatics (n=5, 6). 2OTf-column [n] aromatics (n=5, 6) are used as substrates. The optimal conditions for high yield and high ee value are obtained by screening the reaction conditions of asymmetric catalytic Suzuki coupling reaction. The reaction conditions are relatively mild, and the obtained products are stable in the air and easy to separate and purify, which solves the difficult problems in the preparation and separation of chiral columnar aromatics. In addition, the obtained chiral columnar aromatics have fluorescence and can be used as CPL active materials.

[0042] The technical solution of the present invention is further described in detail below through the accompanying drawings and embodiments. BRIEF DESCRIPTION OF THE DRAWINGS

[0043] Figure 1 This is a functionalized planar chiral columnar aromatic hydrocarbon embodiment 4 of the present invention. 1 HNMR spectrum;

[0044] Figure 2 This is a functionalized planar chiral columnar aromatic hydrocarbon embodiment 4 of the present invention. 13 CNMR spectrum;

[0045] Figure 3 This is the HPLC spectrum of Example 4 of a functionalized planar chiral columnar aromatic hydrocarbon of the present invention;

[0046] Figure 4 This is an X-ray single crystal diffraction structure diagram of Example 10 of a functionalized planar chiral pillar aromatic hydrocarbon of the present invention;

[0047] Figure 5 It is the ultraviolet absorption spectra of Examples 6, 7, 10, 11, 12 and 13 of a functionalized planar chiral pillar aromatic hydrocarbon of the present invention;

[0048] Figure 6 It is the fluorescence emission spectra of Examples 6, 7, 10, 11, 12 and 13 of a functionalized planar chiral pillar aromatic hydrocarbon of the present invention. DETAILED DESCRIPTION

[0049] The technical solution of the present invention is further described below through the accompanying drawings and embodiments.

[0050] Unless otherwise defined, technical or scientific terms used in the present invention shall have the common meanings understood by one having ordinary skills in the field to which the present invention belongs.

[0051] Example 1

[0052] Preparation of compound VII (corresponding to R in the structural formula VII 3 For -CH3), the reaction formula is as follows:

[0053]

[0054] The specific preparation method is:

[0055] In a 500 mL round-bottom flask equipped with a stirrer, (1a) (1.5 g, 2.0 mmol, 1.0 equiv.) and 200 mL of dichloromethane were added and stirred at room temperature until all dissolved. Cerium ammonium nitrate (2.2 g, 4.0 mmol, 2.0 equiv.) was taken into a sample bottle, and water (2.0 mL) was added until completely dissolved. The aqueous solution of cerium ammonium nitrate was slowly added dropwise to the flask under stirring, and stirred at room temperature for 10 min. After the reaction was completed, water was added to the reaction system to quench the reaction, and dichloromethane was used for extraction three times. The organic phases were combined, dried over anhydrous sodium sulfate, concentrated on a rotary evaporator, and separated by column chromatography (eluent: dichloromethane / petroleum ether = 4 / 1) to obtain 0.65 g of an orange-red solid (1b) with a yield of 45.3%. The crude product had no characterization data and could be directly used for the next step.

[0056] In a 250 mL round-bottom flask equipped with a stirrer, (1b) (1.08 g, 1.5 mmol, 1.0 equiv.) and CH2Cl2 (60 mL) were added and stirred at room temperature to dissolve them completely. Sodium dithionite (5.23 g, 30.0 mmol, 20 equiv.) was added to a sample bottle and dissolved in water (20.0 mL). Under stirring, an aqueous sodium dithionite solution was slowly added dropwise to the flask. The reaction was carried out at room temperature for 12 h. After recrystallization, 1.099 g of a white solid product (1c) was obtained with a yield of 87.5%. The crude product had no characterization data and could be directly used for the next step.

[0057] A 250 mL flask equipped with a stirrer was added with (1c) (0.175 g, 0.24 mmol, 1.0 equiv.), 30 mL CH2Cl2, and pyridine (0.3 mL, 0.72 mmol, 3.0 equiv.). The reaction system was transferred to 0°C and stirred for 10 min, and Tf2O (0.5 mL, 0.576 mmol, 2.4 equiv.) was added. The reaction system was transferred to room temperature and reacted for 12 h. After the reaction was completed, the reaction was quenched with dilute hydrochloric acid, extracted three times with water, and three times with dichloromethane. The organic phases were combined and transferred to a 250 mL conical flask, anhydrous sodium sulfate was added to remove moisture, filtered, and concentrated. After column chromatography (eluent: petroleum ether / ethyl acetate = 8 / 1), the product was concentrated to obtain 116 mg of compound VII as a white solid with a yield of 48.5%. The crude product had no characterization data and could be directly subjected to the next step.

[0058] Example 2

[0059] Preparation of compound VIII (corresponding to R in the structural formula VIII 1 For -CH2CH3), the reaction formula is as follows:

[0060]

[0061] The specific preparation method is:

[0062] The difference from Example 1 is that (2a) (2.1 g, 2.0 mmol, 1.0 equiv.) was added to a 500 mL round-bottom flask equipped with a stirrer to obtain 0.85 g of an orange-red solid (2b) with a yield of 41.3%. The crude product has no characterization data and can be directly used for the next step reaction.

[0063] After recrystallization, 1.4 g of white solid product (2c) was obtained with a yield of 90.5%. The crude product had no characterization data and could be directly used for the next step reaction.

[0064] The mixture was concentrated to give 174.7 mg of compound VIII as a white solid with a yield of 47.5%. The crude product had no characterization data and could be directly used for the next step.

[0065] Example 3

[0066] Preparation of a single-site functionalized pillar aromatic derivative: Compound Va (corresponding to R in the structural formula V 1 For -OMe), the reaction formula is as follows:

[0067]

[0068] The specific preparation method is:

[0069] Compound VII (987.0 mg, 1.0 mmol, 2.0 equiv), 4-methylphenylboronic acid (152.0 mg, 1.0 mmol, 2.0 equiv), Pd(PPh3)4 (231.1 mg, 10 mol%), Na3PO4 (820 mg, 5.0 mmol, 5.0 equiv.) were added to a 100 mL Shrek tube equipped with a stirrer, and 40 mL of oxygen-free tetrahydrofuran was added, and stirred at 50 ° C for 24 h under a nitrogen atmosphere. After cooling to room temperature, the mixture was dried by spin drying, and the residue was separated by column chromatography on 230-400 mesh silica gel with petroleum ether: diethyl ether = 20:1 to obtain 727.1 mg of compound Va, with a yield of 77%.

[0070] 1HNMR(500MHz,Chloroform-d)δ7.19(s,1H),7.07(s,1H),6.94(d,J=8.1Hz,2 H),6.82(d,J=8.2Hz,2H),6.77(s,2H),6.75(s,2H),6.71(s,1H),6.66(s,2H ),5.84(s,1H),3.89–3.77(m,11H),3.72(s,2H),3.71(s,3H),3.68(s,3H),3 .66(s,3H),3.62(s,3H),3.60(s,3H),3.54(s,3H),3.50(s,3H),3.45(s,3H). 13 CNMR(126MHz,Chloroform-d)δ158.8,151.2,151.1,150.9,150.7,150.4,147.4,140.9,13 9.8,133.9,133.4,130.7,130.5,129.7,128.8,128.7,128.6,128.5,128.1,127.2,125.5,1 22.6,118.8(q,J=318.8Hz),114.7,114.4,114.3,114.2,114.0,113.9,113.8,113.7,113. 3,56.2,56.04,55.95,55.9,55.8,55.54,55.5,55.42,55.38,33.0,31.3,30.2,29.6,29.5. 19 FNMR(376MHz,Chloroform-d)δ-73.8.

[0071] From the above, it can be seen that the structure of the above compound is correct, which is the compound Va shown.

[0072] Example 4

[0073] Preparation of a bifunctional chiral pillar aromatic derivative: Compound Ia, the reaction formula is as follows:

[0074]

[0075] The specific preparation method is:

[0076] Compound VII (49.3 mg, 0.05 mmol, 1.0 equiv), 4-methoxyphenylboronic acid 4a (33.8 mg, 0.25 mmol, 5.0 equiv), Pd(OAc)2 (2.2 mg, 20 mol%), Na3PO4 (81.9 mg, 0.5 mmol, 10.0 equiv), L22 (10.6 mg, 40 mol%), and 1,4-dioxane (2.0 mL) were added to a 100 mL Shrek tube equipped with a stirrer, and stirred at 80 ° C for 24 h under a nitrogen atmosphere. After cooling to room temperature, the mixture was dried by spin drying, and the residue was separated by column chromatography on 230-400 mesh silica gel with petroleum ether: diethyl ether = 20:1 to obtain 42.1 mg of compound Ia, with a yield of 93% and an ee value of 98%.

[0077] like Figure 1 and Figure 2 As shown, they are respectively 1 HNMR spectra and 13 CNMR spectrum:

[0078] 1 HNMR(500MHz,Chloroform-d)δ6.96(s,2H),6.92(d,J=8.0Hz,4H),6.75(d,J=8.0H z,4H),6.71(s,4H),6.54(s,2H),5.88(s,2H),3.88(d,J=14.1Hz,2H),3.86(s,2H),3.84(s,6 H),3.78(d,J=14.1Hz,2H),3.74(s,4H),3.67(s,6H),3.55(s,6H),3.37(s,6H),3.35(s,6H). 13 CNMR(126MHz,Chloroform-d)δ158.4,151.3,151.2,151.0,150.8,139.9,136.7,134.9,132.4,130.4,128.8,128.7,1 28.6,128.5,114.5,114.4,114.3,114.0,113.5,56.21,56.17,55.9,55.7,55.4,33.8,30.3,29.6.HRMS(MALDITOF):C 57 H 58 KO 10 [M+K] + :941.3662,found:941.3622.

[0079] From the above, it can be seen that the structure of the above compound is correct, which is the compound Ia shown.

[0080] like Figure 3 The HPLC separation spectrum is shown in Table 1, indicating that the ee value of compound Ia is 98.6%, which has a high ee value.

[0081] Table 1 HPLC spectrum test data of compound Ia

[0082]

[0083] Example 5

[0084] Preparation of compound Ib, the reaction formula is as follows:

[0085]

[0086] The specific preparation method is:

[0087] The difference from Example 4 is that phenylboronic acid 4a (33.8 mg, 0.25 mmol, 5.0 equiv) is replaced by phenylboronic acid 4b (38.0 mg, 0.25 mmol, 5.0 equiv), and 37.1 mg of compound Ib is obtained with a yield of 82% and an ee value of 96%.

[0088] 1 HNMR(500MHz,Chloroform-d)δ7.02(d,J=7.6Hz,4H),6.98(s,2H),6.91(d,J=7.6H z,4H),6.72(s,2H),6.70(s,2H),6.50(s,2H),5.88(s,2H),3.90(d,J=14.3Hz,2H),3.87(s,2H),3. 77(d,J=14.4Hz,2H),3.74(s,4H),3.68(s,6H),3.54(s,6H),3.34(s,6H),3.32(s,6H),2.38(s,6H). 13 CNMR(126MHz,Chloroform-d)δ151.3,151.2,151.0,150.8,140.3,139.6,136.6,135.9,132.4,129.4,128.8,128.7,128 .6,128.5,114.6,114.3,114.1,56.2,55.8,55.6,33.7,30.2,29.6,21.3.HRMS(MALDITOF):exactmasscalculatedfor:C 57 H 58 KO8[M+K] +:909.3763, front:909.3740.

[0089] From the above, it can be seen that the structure of the above compound is correct, which is the compound Ib shown.

[0090] Example 6

[0091] Preparation of compound Ic, the reaction formula is as follows:

[0092]

[0093] The specific preparation method is:

[0094] The difference from Example 4 is that phenylboronic acid 4a (33.8 mg, 0.25 mmol, 5.0 equiv) is replaced by phenylboronic acid 4c (37.5 mg, 0.25 mmol, 5.0 equiv), and 37.0 mg of compound Ic is obtained with a yield of 82% and an ee value of 96%.

[0095] 1 HNMR(500MHz,Chloroform-d)δ7.09(d,J=7.6Hz,4H),7.05(s,2H),6.98(d,J=7.6H z,4H),6.72(s,2H),6.70(s,2H),6.51(s,2H),5.88(s,2H),3.93(d,J=14.1Hz,2H),3.87(s,2H),3.79(d,J=14.2Hz,2H),3.75( d,J=13.5Hz,2H),3.72(d,J=13.5Hz,2H),3.68(s,6H),3.54(s,6H),3.34(s,6H),2.69(q,J=7.6Hz,4H),1.30(t,J=7.5Hz,6H). 13 CNMR(126MHz,Chloroform-d)δ151.3,151.2,151.0,150.8,142.3,140.3,139.8,136.5,132.5,129.5,128.8,128.7,128.6,128.5,12 7.5,114.6,114.4,114.3,114.0,56.2,56.2,55.8,55.7,33.4,30.2,29.7,28.7,15.7.HRMS(MALDITOF):exactmasscalculatedfor:C 59 H 62 KO8[M+K] + :937.4076,found:937.4049.

[0096] From the above, it can be seen that the structure of the above compound is correct, which is the compound Ic shown.

[0097] Example 7

[0098] Compound Id is prepared according to the following reaction formula:

[0099]

[0100] The specific preparation method is:

[0101] The difference from Example 4 is that phenylboronic acid 4a (33.8 mg, 0.25 mmol, 5.0 equiv) is replaced by phenylboronic acid 4d (41.0 mg, 0.25 mmol, 5.0 equiv), and 39.0 mg of compound Id is obtained with a yield of 84% and an ee value of 100%.

[0102] 1 HNMR(500MHz,Chloroform-d)δ7.07(d,J=7.8Hz,4H),7.05(s,2H),6.97(d,J=7.5H z,4H),6.71(s,2H),6.70(s,2H),6.51(s,2H),5.87(s,2H),3.92(d,J=1 4.1Hz,2H),3.86(s,2H),3.79(d,J=14.2Hz,2H),3.75(d,J=13.7Hz,2H), 3.71(d,J=13.7Hz,2H),3.67(s,6H),3.53(s,6H),3.34(s,6H),3.31(s, 6H), 2.62 (t, J = 7.7Hz, 4H), 1.69 (h, J = 7.4Hz, 4H), 1.01 (t, J = 7.3Hz, 6H). 13 CNMR(126MHz,Chloroform-d)δ151.4,151.2,151.1,150.9,140.8,140.4,139.9,136.6,132.5,129.5,128.98,128.90,128.74,128.71,128. 1,114.7,114.5,114.4,114.1,56.3,55.84,55.81,53.46,38.0,33.4,30.3,29.7,24.7,14.1.HRMS(MALDITOF):exactmasscalculatedfor:C 61 H 66 KO8[M+K] + :965.4389,found:965.4372.

[0103] From the above, it can be seen that the structure of the above compound is correct, which is the compound Id shown.

[0104] Example 8

[0105] Preparation of compound Ie, the reaction formula is as follows:

[0106]

[0107] The specific preparation method is:

[0108] The difference from Example 4 is that phenylboronic acid 4a (33.8 mg, 0.25 mmol, 5.0 equiv) is replaced by phenylboronic acid 4e (44.5 mg, 0.25 mmol, 5.0 equiv), and 42.5 mg of compound Ie is obtained with a yield of 89% and an ee value of 98%.

[0109] 1 HNMR(500MHz,Chloroform-d)δ7.36(d,J=7.8Hz,4H),7.20(s,2H),7.11(d,J=7.8H z,4H),6.76(s,2H),6.70(s,2H),6.55(s,2H),5.83(s,2H),3.98(d,J=13.8Hz,2H),3.84(s,2H),3.8 2(d,J=13.8Hz,2H),3.74(s,4H),3.66(s,6H),3.60(s,6H),3.43(s,6H),3.30(s,6H),1.38(s,18H). 13 CNMR(126MHz,Chloroform-d)δ151.3,151.2,150.9,150.8,149.3,140.2,139.6,136.5,132.8,129.4,128.8,128.63,128.55,128.49, 124.5,114.7,114.4,114.2,113.8,56.3,56.2,55.8,55.7,34.6,32.9,31.6,30.2,30.0.HRMS(MALDITOF):exactmasscalculatedfor:C 63 H 70 NaO8[M+Na] + :977.4963,found:977.4925.

[0110] From the above, it can be seen that the structure of the above compound is correct, which is the compound Ie shown.

[0111] Example 9

[0112] Preparation of compound If, the reaction formula is as follows:

[0113]

[0114] The specific preparation method is:

[0115] The difference from Example 4 is that phenylboronic acid 4a (33.8 mg, 0.25 mmol, 5.0 equiv) is replaced by phenylboronic acid 4f (57.0 mg, 0.25 mmol, 5.0 equiv), and 34.3 mg of compound If can be obtained with a yield of 65% and an ee value of 96%.

[0116] 1 HNMR(500MHz,Chloroform-d)δ7.50(d,J=7.5Hz,4H),7.44(t,J=7.5Hz,4H),7.37(t,J=7.3Hz,2H),6.96(s,2H),6.92(d,J=8.1Hz,4H),6.8 2(d,J=8.2Hz,4H),6.71(s,2H),6.69(s,2H),6.54(s,2H),5.90(s,2H),5.09(s,4H),3.89(d,J=14.2Hz,2H),3.88(s,2H),3.79(d,J=14.2H z,2H),3.75(s,4H),3.63(s,6H),3.53(s,6H),3.37(s,6H),3.34(s,6H). 13 CNMR(126MHz,Chl oroform-d)δ157.6,151.3,151.1,151.0,150.8,139.9,137.3,136.7,135.2,132.3,130.4,128.78,128.75,128.70,128.6,128.5,128.2, 127.7,114.51,114.46,114.4,114.3,114.0,70.2,56.3,56.2,55.9,55.7,33.8,30.3,29.5.HRMS(MALDITOF):exactmasscalculatedfor:C 69 H 66 KO 10 [M+K] + :1093.4288,found:1093.4258.

[0117] From the above, it can be seen that the structure of the above compound is correct, which is the compound If shown.

[0118] Example 10

[0119] Preparation of compound Ig, the reaction formula is as follows:

[0120]

[0121] The specific preparation method is:

[0122] The difference from Example 4 is that phenylboronic acid 4a (33.8 mg, 0.25 mmol, 5.0 equiv) is replaced by phenylboronic acid 4g (49.5 mg, 0.25 mmol, 5.0 equiv), and 40.9 mg of compound Ig is obtained with a yield of 82% and an ee value of 97%.

[0123] 1 HNMR(500MHz,Chloroform-d)δ7.66(d,J=7.3Hz,4H),7.52-7.49(m,8H),7.39(t,J=7. 5Hz,2H),7.12(d,J=8.2Hz,4H),7.08(s,2H),6.72(s,2H),6.71(s,2H),6.55(s,2H),5 .93(s,2H),3.98(d,J=14.3Hz,2H),3.89(s,2H),3.86(d,J=14.4Hz,2H),3.77(d,J=14 .0Hz,2H),3.74(d,J=14.0Hz,2H),3.65(s,6H),3.55(s,6H),3.37(s,6H),3.32(s,6H). 13 CNMR(126MHz,Chl oroform-d)δ151.3,151.2,151.1,150.8,141.5,141.0,140.2,139.3,136.7,132.4,129.9,129.0,128.7,128.3,127.4,127.1 ,126.7,114.6,114.4,114.3,114.0,56.23,56.20,55.8,55.7,33.9,30.3,29.6.HRMS(MALDITOF):exactmasscalculatedfor:C 67 H 62 KO8[M+K] + :1033.4076,found:1033.4030.

[0124] From the above, it can be seen that the structure of the above compound is correct, which is the compound Ig shown.

[0125] Embodiment 11

[0126] Compound Ih was prepared according to the following reaction formula:

[0127]

[0128] The specific preparation method is:

[0129] The difference from Example 4 is that phenylboronic acid 4a (33.8 mg, 0.25 mmol, 5.0 equiv) is replaced by phenylboronic acid 4h (43.0 mg, 0.25 mmol, 5.0 equiv), and 32.5 mg of compound Ih is obtained with a yield of 69% and an ee value of 96%.

[0130] 1 HNMR(500MHz,Chloroform-d)δ7.87-7.86(m,2H),7.75-7.72(m,2H),7.60(s,2H),7.56(d,J= 8.5Hz,2H),7.51-7.49(m,4H),7.11(s,2H),7.05(d,J=8.5Hz,2H),6.77(s,2H),6.73(s,2H), 6.55(s,2H),5.76(s,2H),3.96(d,J=14.3Hz,2H),3.94(s,2H),3.87(d,J=14.3Hz,2H),3.75( d,J=13.5Hz,2H),3.72(s,6H),3.68(d,J=13.5Hz,2H),3.54(s,6H),3.31(s,6H),3.01(s,6H). 13 CNMR(126MHz,Chloroform-d)δ151.4,151.2,151.0,150.7,140.5,140.0,136.9,133.3,132.5,132.3,128.8,128.6,128.2,128.1,127.83 ,127.78,127.6,126.1,125.8,114.5,114.42,114.39,113.9,56.3,56.1,55.8,55.2,34.1,30.2,29.3.HRMS(MALDITOF):exactmasscalcul atedfor:C 63 H 58 KO8[M+K] + :981.3763,found:981.3740.

[0131] From the above, it can be seen that the structure of the above compound is correct, which is the compound Ih shown.

[0132] Example 12

[0133] Preparation of compound Ii, the reaction formula is as follows:

[0134]

[0135] The specific preparation method is:

[0136] The difference from Example 4 is that phenylboronic acid 4a (33.8 mg, 0.25 mmol, 5.0 equiv) is replaced by phenylboronic acid 4h (43.0 mg, 0.25 mmol, 5.0 equiv), and 45.3 mg of compound Ii can be obtained with a yield of 87% and an ee value of 98%.

[0137] 1 HNMR(500MHz,Chloroform-d)δ8.45(s,2H),8.36(s,2H),8.07–8.02(m,4H),7.83(s,2H),7.62 (d,J=8.6Hz,2H),7.52–7.49(m,4H),7.15(s,2H),6.95(d,J=8.6Hz,2H),6.79(s,2H),6.75(s,2 H),6.57(s,2H),5.83(s,2H),4.03(d,J=14.4Hz,2H),4.00(s,2H),3.93(d,J=14.4Hz,2H),3.76 (d,J=13.6Hz,2H),3.75(s,6H),3.68(d,J=13.6Hz,2H),3.54(s,6H),3.32(s,6H),2.90(s,6H). 13 CNMR(126MHz,Chloroform-d)δ151.4,151.2,151.1,150.7,140.5,139.5,137.1,1 32.4,132.0,131.8,131.7,130.7,128.9,128.8,128.7,128.4,128.24,128.15,12 8.0,127.9,127.5,126.2,126.1,125.6,125.4,114.6,114.5,114.4,113.9,56.3, 56.2,55.9,55.1,34.3,30.2,29.2.HRMS(MALDITOF):exactmasscalculatedfor:C 71 H 62 KO8[M+K] + :1081.4076,found:1081.4050.

[0138] From the above, it can be seen that the structure of the above compound is correct, which is the compound Ii shown.

[0139] Example 13

[0140] Compound Ij is prepared according to the following reaction formula:

[0141]

[0142] The specific preparation method is:

[0143] The difference from Example 4 is that phenylboronic acid 4a (33.8 mg, 0.25 mmol, 5.0 equiv) is replaced by phenylboronic acid 4j (62.0 mg, 0.25 mmol, 5.0 equiv), and 44.4 mg of compound Ij can be obtained with a yield of 80% and an ee value of 99%.

[0144] 1 HNMR(500MHz,Chloroform-d)δ8.25(d,J=7.6Hz,4H),8.15(d,J=8.9Hz,4H),8.06 (t,J=7.6Hz,2H),8.03–7.94(m,8H),7.46(s,2H),6.87(s,2H),6.79(s,2H),6.59( s,2H),5.61(s,2H),4.08(d,J=14.1Hz,2H),4.01–3.98(m,4H),3.79(s,6H),3.77 (d,J=14.0Hz,2H),3.67(d,J=13.8Hz,2H),3.60(s,6H),3.38(s,6H),2.83(s,6H). 13 CNMR(126MHz,Chloroform-d)δ151.5,151.3,150.9,150.6,140.9,140.3,136.9,133.3,131.2,131.0,129.0,128.7,128.5,1 28.1,127.8,127.6,126.4,126.0,125.2,124.7,123.6,114.7,114.6,114.1,113.6,56.4,56.3,55.6,55.0,33.8,30.3,29.5.

[0145] Embodiment 14

[0146] Compound Ik is prepared according to the following reaction formula:

[0147]

[0148] The specific preparation method is:

[0149] The difference from Example 4 is that phenylboronic acid 4a (33.8 mg, 0.25 mmol, 5.0 equiv) is replaced by phenylboronic acid 4k (35.0 mg, 0.25 mmol, 5.0 equiv), and 35.2 mg of compound Ik can be obtained with a yield of 80% and an ee value of 98%.

[0150] 1 HNMR(500MHz,Chloroform-d)δ6.87–6.83(m,8H),6.81(s,2H),6.79(s,2H),6.73(s,2H),6.53(s,2H),5.96(s,2 H),3.89(s,2H),3.88(d,J=13.5Hz,2H),3.80–3.72(m,6H),3.71(s,6H),3.60(s,6H),3.43(s,6H),3.31(s,6H). 13 CNMR(126MHz,Chloroform-d)δ161.79(d,J=245.7Hz),151.1,151.0,150.8,139.7,138.12,138.09,137.0,132.0,130. 64,130.58,129.1,128.7,128.0,114.9,114.7,114.3,114.2,114.14,114.11,56.1,56.0,55.8,55.7,33.9,30.0,29.7. 19 F NMR(471MHz,Chloroform-d)δ-116.77(p,J=7.1Hz).HRMS(MALDITOF):exactmassc alculatedfor:C 55 H 52 F2KO8[M+K] + :917.3262,found:917.3237.

[0151] From the above, it can be seen that the structure of the above compound is correct, which is the compound Ik shown.

[0152] Embodiment 15

[0153] Preparation of compound I1, the reaction formula is as follows:

[0154]

[0155] The specific preparation method is:

[0156] The difference from Example 4 is that phenylboronic acid 4a (33.8 mg, 0.25 mmol, 5.0 equiv) is replaced by phenylboronic acid 4l (36.8 mg, 0.25 mmol, 5.0 equiv), and 44.0 mg of compound Il is obtained with a yield of 76% and an ee value of 96%.

[0157] 1 HNMR(500MHz,Chloroform-d)δ7.37(d,J=7.9Hz,4H),6.94(d,J=7.8Hz,4H),6.81(s,2H),6.72(s,2H),6.70(s,2H),6.51(s,2H),5.9 9(s,2H),3.91(s,2H),3.87(d,J=15.0Hz,2H),3.75(d,J=2.1Hz,4H),3.70(d,J=19.4Hz,7H),3.64(s,7H),3.47(s,6H),3.27(s,6H). 13 CNMR(126MHz,Chloroform-d)δ151.3,151.1,151.0,150.8,146.7,139.6,137.2,131.9,131.4,129.71,129.68,128.79,128.75,127.2 ,119.2,114.5,114.2,114.11,114.06,110.4,56.3,56.2,56.0,55.6,33.9,30.0,29.8.HRMS(MALDITOF):exactmasscalculatedfor:C 57 H 52 N2KO8[M+K] + :931.3355,found:931.3371.

[0158] From the above, it can be seen that the above compound structure is correct, which is the compound I1 shown.

[0159] Embodiment 17

[0160] Preparation of compound Im, the reaction formula is as follows:

[0161]

[0162] The specific preparation method is:

[0163] The difference from Example 4 is that phenylboronic acid 4a (33.8 mg, 0.25 mmol, 5.0 equiv) is replaced by phenylboronic acid 4m (41.8 mg, 0.25 mmol, 5.0 equiv), and 36.4 mg of compound Im is obtained with a yield of 78% and an ee value of 98%.

[0164] 1 HNMR(500MHz,Chloroform-d)δ8.01(d,J=8.7Hz,4H),7.04(d,J=8.2Hz,4H),6.85(s,2H),6.82(s,2H),6.71(s,2H),6.51(s,2H),6.01(s,2H),3.91(s,2 H),3.90(d,J=15.0Hz,2H),3.77(d,J=13.5Hz,2H),3.73(d,J=13.5Hz,2H), 3.70(s,6H),3.69(d,J=15.0Hz,2H),3.61(s,6H),3.42(s,6H),3.30(s,6H). 13 CNMR(126MHz,Chloroform-d)δ151.4,151.1,150.9,150.8,148.7,146.9,139.4,137.3,131.5,129.9,129.8,128.9,128. 7,127.0,123.3,114.7,114.3,114.1,114.0,56.2,56.0,55.5,33.7,30.0.HRMS(MALDITOF):exactmasscalculatedfor:C 55 H 52 N2KO 12 [M+K] + :971.3152,found:971.3115.

[0165] From the above, it can be seen that the structure of the above compound is correct, which is the compound Im shown.

[0166] Embodiment 18

[0167] Preparation of compound In, the reaction formula is as follows:

[0168]

[0169] The specific preparation method is:

[0170] The difference from Example 4 is that phenylboronic acid 4a (33.8 mg, 0.25 mmol, 5.0 equiv) is replaced by phenylboronic acid 4n (47.5 mg, 0.25 mmol, 5.0 equiv), and 34.3 mg of compound In can be obtained with a yield of 70% and an ee value of 97%.

[0171] 1 HNMR(500MHz,Chloroform-d)δ7.45(d,J=7.8Hz,4H),7.05(d,J=7.8Hz,4H),6.88(s,2H),6.75(s,4H),6.54(s,2H),5.93(s,2H),3.89 (s,2H),3.86(d,J=14.4Hz,2H),3.78(d,J=14.4Hz,2H),3.77(s,2H),3.74(s,2H),3.72(s,6H),3.55(s,6H),3.41(s,6H),3.31(s,6H). 13 CNMR(126MHz,Chloroform-d)δ151.23,151.19,151.0,150.8,145.8,139.8,136.9,131.9,129.6,129.3,128.82(q,J=32.1Hz), 128.81,128.6,127.5,125.0(q,J=3.8Hz),124.5(q,J=272.8Hz),114.4,114.3,114.0,56.2,56.0,55.9,55.6,33.8,30.2,29.6. 19 FNMR(471MHz,Chloroform-d)δ-62.23.HRMS(MALDITOF):exactmasscalculatedfor:C 57 H 52 F6NaO8[M+Na] + :1001.3459,found:1001.3450.

[0172] From the above, it can be seen that the structure of the above compound is correct, which is the compound In shown.

[0173] Embodiment 19

[0174] Compound Io is prepared according to the following reaction formula:

[0175]

[0176] The specific preparation method is:

[0177] The difference from Example 4 is that phenylboronic acid 4a (33.8 mg, 0.25 mmol, 5.0 equiv) is replaced by phenylboronic acid 4n (47.5 mg, 0.25 mmol, 5.0 equiv), and 42.8 mg of compound Io is obtained with a yield of 60% and an ee value of 96%.

[0178] 1 HNMR(500MHz,Chloroform-d)δ7.75(s,2H),7.71–7.69(m,4H),7.66–7.64(m,4H),7.6 2–7.45(m,16H),7.43(d,J=7.3Hz,2H),7.36–7.34(m,4H),7.16(s,2H),6.82(s,2H),6 .77(s,2H),6.62(s,2H),6.34(s,2H),5.69(s,2H),3.88(d,J=13.9Hz,2H),3.81(s,2H ),3.75–3.70(m,2H),3.69(s,4H),3.58(s,6H),3.55(s,6H),3.10(s,6H),3.02(s,6H). 13 CNMR(126MHz,Chlor oform-d)δ151.2,151.1,150.7,150.3,140.3,139.3,139.0,138.7,137.4,137.0,136.9, 132.7,131.5,131.44,131.37,131.3,130.3,130.0,129.7,128.8,128.7,128.6,128.63, 128.61,128.57,128.5,128.3,128.0,127.9,127.72,127.68,127.11,127.08,126.8,126.5,125.3,125.2,114.69,113.8,113.7,113.5,56.3,55.9,55.4,55.3,33.3,30.1,29.7.

[0179] Embodiment 20

[0180] Preparation of compound Ip (corresponding to R in formula I 1 For -CH3), the reaction formula is as follows:

[0181]

[0182] The specific preparation method is:

[0183] The difference from Example 4 is that phenylboronic acid 4a (33.8 mg, 0.25 mmol, 5.0 equiv) is replaced by phenylboronic acid 4p (93.55 mg, 0.25 mmol, 5.0 equiv), and 41.9 mg of compound Ip is obtained with a yield of 62% and an ee value of 96%.

[0184] 1 HNMR(500MHz,Chloroform-d)δ7.18–7.03(m,32H),7.01(d,J=7.8Hz,4H),6.92(d,J=7.8Hz,4H),6.71(s,2H),6.66(s,2H),6.61(s,2H ),5.90(s,2H),3.84–3.79(m,6H),3.76(d,J=13.6Hz,2H),3.70(d,J=13.6Hz,2H),3.57(s,6H),3.51(s,6H),3.47(s,6H),3.26(s,6H). 13 CN MR(126MHz,Chloroform-d)δ151.2,151.106,151.2,150.8,143.89,143.86 ,142.0,141.3,140.8,140.7,140.1,136.4,132.6,131.51,131.48,131.0,1 29.0,128.8,128.70,128.68,128.3,127.9,127.84,127.80,126.7,126.64 ,126.60,114.5,114.3,114.22,114.19,56.2,56.0,55.8,32.2,30.6,29.6.

[0185] Embodiment 21

[0186] Preparation of compound Iq, the reaction formula is as follows:

[0187]

[0188] The specific preparation method is:

[0189] The difference from Example 4 is that phenylboronic acid 4a (33.8 mg, 0.25 mmol, 5.0 equiv) is replaced by phenylboronic acid 4q (49.8 mg, 0.25 mmol, 5.0 equiv), and 40.0 mg of compound Iq can be obtained with a yield of 80% and an ee value of 96%.

[0190] 1HNMR(500MHz,Chloroform-d)δ8.72(d,J=6.2Hz,4H),7.59(d,J=6.2Hz,4H),7.47(d,J=7.8Hz,4H),7.08(d,J=7.7Hz,4H),6.96(s,2H),6.70(s,2H ),6.63(s,2H),6.56(s,2H),5.91(s,2H),3.91(s,2H),3.91–3.81(m,4H) ,3.78–3.72(m,4H),3.60(s,6H),3.51(s,6H),3.33(s,6H),3.31(s,6H). 13 CNMR(126MHz,Chloroform-d)δ151.4,151.2,151.3,150.9,150.4,148.3,143.4,140.0,136.8,136.1,132.1,130.1,129. 0,128.8,128.7,128.1,127.9,127.7,126.6,121.5,114.7,114.5,114.4,114.0,56.4,56.1,55.9,55.7,34.4,30.3,29.3.

[0191] Embodiment 22

[0192] Preparation of compound Ir, the reaction formula is as follows:

[0193]

[0194] The specific preparation method is:

[0195] The difference from Example 4 is that phenylboronic acid 4a (33.8 mg, 0.25 mmol, 5.0 equiv) is replaced by phenylboronic acid 4r (47.5 mg, 0.25 mmol, 5.0 equiv), and 88.3 mg of compound Ir is obtained with a yield of 80% and an ee value of 98%.

[0196] 1HNMR(500MHz,Chloroform-d)δ8.85(s,4H),8.78(d,J=4.8Hz,4H),8.73(d,J=7.9H z,4H),7.91(t,J=7.8Hz,4H),7.87(d,J=7.8Hz,4H),7.42–7.33(m,4H),7.25(d, J=4.8Hz,4H),7.17(s,2H),6.89(s,2H),6.79(s,2H),6.61(s,2H),5.96(s,2H), 3.99(d,J=14.2Hz,2H),3.92(s,2H),3.91(d,J=14.2Hz,2H),3.80(d,J=13.6Hz, 2H),3.74(d,J=13.5Hz,2H),3.69(s,6H),3.63(s,6H),3.45(s,6H),3.39(s,6H). 13 CNMR(126MHz,Chloroform-d)δ156.4,156.2,151.3,151.2,151.0,150.8,150.1,149.3,143.4,140.1,137.0,136.8,136.7,132. 5,130.2,128.9,128.6,128.0,127.0,124.0,121.5,118.9,114.6,114.2,114.1,114.0,56.2,56.1,55.8,55.7,33.6,30.2,29.5.

[0197] Embodiment 23

[0198] Preparation of compound IIa, the reaction formula is as follows:

[0199]

[0200] The specific preparation method is:

[0201] In a 100 mL Shrek tube equipped with a stirrer, add formula Va (47.2 mg, 0.05 mmol, 1.0 equiv), phenylboronic acid 4k (35.0 mg, 0.25 mmol, 5.0 equiv), Pd(OAc)2 (2.2 mg, 20 mol%), Na3PO4 (81.9 mg, 0.5 mmol, 10.0 equiv), L22 (10.6 mg, 40 mol%), and then add 1,4-dioxane (2.0 mL), and stir at 80 ° C for 24 h under a nitrogen atmosphere. After cooling to room temperature, spin dry, the residue is separated by column chromatography on 230-400 mesh silica gel with petroleum ether: diethyl ether = 10:1, and the product compound represented by formula (IIa) 35.7 mg can be obtained, with a yield of 80% and an ee value of 99%.

[0202] 1 HNMR(500MHz,Chloroform-d)δ7.06(s,2H),7.05(s,1H),6.83(d,J=8.1Hz,2H),6.80–6.68(m,8H),6.67(s,1H),6.54(s,1H),6.53(s,1H),6.03(s, 1H),5.84(s,1H),3.94–3.84(m,7H),3.81–3.70(m,9H),3.67(s,3H),3.62 (s,3H),3.55(s,3H),3.42(s,3H),3.39(s,3H),3.34(s,3H),3.31(s,3H). 13 CNMR(126MHz,Chloroform-d)δ161.7(d,J=244.24Hz),158.5,151.20,151.17,151.15,151.1, 151.0,150.94,150.90,150.7,140.2,139.4,136.9,136.8,134.6,132.4,131.9,130.6,130.49 ,130.46,129.0,128.8,128.7,128.6,128.4,128.1,114.7,114.64,114.58,114.4,114.3,114.14,114.07,113.8,113.6,56.19,56.16,56.11,55.8,55.6,55.4,34.0,33.7,30.2,30.0,29.6.

[0203] Embodiment 24

[0204] Preparation of compound IIb (corresponding to R in structural formula II 1 For -CH3), the reaction formula is as follows:

[0205]

[0206] The specific preparation method is:

[0207] The difference from Example 23 is that phenylboronic acid 4k (47.5 mg, 0.25 mmol, 5.0 equiv) is replaced by phenylboronic acid 4n (44.5 mg, 0.25 mmol, 5.0 equiv), and 37.1 mg of compound IIb is obtained with a yield of 79% and an ee value of 98%.

[0208] 1 HNMR(500MHz,Chloroform-d)δ7.35(d,J=7.9Hz,2H),7.09(s,1H),7.07(d,J=8.6H z,2H),6.90(d,J=7.8Hz,2H),6.85(d,J=8.4Hz,2H),6.76(s,1H),6.74(s, 1H),6.73(s,1H),6.73(s,1H),6.71(s,1H),6.55(s,1H),6.54(s,1H),6.0 3(s,1H),5.81(s,1H),3.92–3.73(m,13H),3.72(s,3H),3.69(s,3H),3.60 (s,3H),3.51(s,3H),3.44(s,3H),3.36(s,3H),3.35(s,3H),3.30(s,3H). 13 CNMR(126MHz,Chloroform-d)δ158.6,151.3,151.2,151.14,151.06,150.9,150.7,146.2,140.6,139 .1,137.1,136.5,134.4,132.6,131.6,130.5,129.5,129.0,128.9,128.8,128.71,128.69,128.63,12 8.5(q,J=31.5Hz),128.2,127.8,124.6(q,J=272.2Hz),114.5,114.34,114.26,114.23,114.16,113. 8,113.6,56.22,56.16,56.1,56.0,55.9,55.8,55.65,55.61,55.41,33.99,33.6,30.24,30.21,29.6.

[0209] Embodiment 25

[0210] Preparation of compound IIc (corresponding to R in structural formula II1 For -CH3), the reaction formula is as follows:

[0211]

[0212] The specific preparation method is:

[0213] The difference from Example 23 is that phenylboronic acid 4k (47.5 mg, 0.25 mmol, 5.0 equiv) is replaced by phenylboronic acid 4e (44.5 mg, 0.25 mmol, 5.0 equiv), and 34.5 mg of compound IIc is obtained with a yield of 74% and an ee value of 96%.

[0214] 1 HNMR(500MHz,Chloroform-d)δ7.40(s,1H),7.38(s,1H),7.20(s,1H),7.18(s,1H),7 .17(s,1H),6.95(s,1H),6.86(d,J=7.7Hz,2H),6.79–6.72(m,5H),6.69(s,1H),6.55( s,2H),5.95(s,1H),5.81(s,1H),4.01–3.79(m,9H),3.77(s,2H),3.74(s,2H),3.71( s,3H),3.65(s,3H),3.60(s,3H),3.57(s,3H),3.43(s,3H),3.36(s,9H),1.39(s,9H). 13 CNMR(126MHz,Chloroform-d)δ158.3,151.3,151.2,151.1,151.0,150.9,150.8,150.7,140.0,139.4 ,136.7,136.5,135.0,132.8,132.3,130.4,129.4,128.80,128.77,128.72,128.69,128.56,128.53, 128.51,128.4,126.5,125.0,114.9,114.50,114.47,114.3,114.21,114.16,114.1,113.7,113.4,56.4,56.2,56.11,56.07,55.9,55.8,55.7,55.5,55.4,34.6,33.8,33.0,31.7,31.6,30.3,30.1,29.7.

[0215] Embodiment 26

[0216] Preparation of compound IId, the reaction formula is as follows:

[0217]

[0218] The specific preparation method is:

[0219] The difference from Example 23 is that phenylboronic acid 4k (47.5 mg, 0.25 mmol, 5.0 equiv) is replaced by phenylboronic acid 4h (43.0 mg, 0.25 mmol, 5.0 equiv), to obtain 41.0 mg of compound IId with a yield of 86% and an ee value of 96%.

[0220] 1 HNMR(500MHz,Chloroform-d)δ8.43(s,1H),8.33(s,1H),8.09–7.99(m,2H),7.77(s,1H),7.57–7.46(m,3H),7. 12(s,1H),7.06(d,J=8.1Hz,2H),7.03(s,1H),6.84(d,J=8.2Hz,2H),6.81(d,J=8.6Hz,1H),6.78(s,1H),6.77( s,1H),6.76(s,1H),6.75(s,1H),6.60(s,1H),6.55(s,1H),6.00(s,1H),5.74(s,1H),4.03–4.01(m,2H),3.96– 3.84(m,8H),3.84–3.64(m,12H),3.59(s,3H),3.53(s,3H),3.43(s,3H),3.42(s,3H),3.26(s,3H),2.81(s,3H). 13 CNMR(126MHz,Chl oroform-d)δ158.5,151.34,151.3,151.2,151.1,151.0,150.9,150.7,140.3,140.2,139.6,136.9, 134.8,132.6,132.2,132.0,131.8,131.7,130.7,130.5,128.9,128.82,128.78,128.7,128.5,128.4 4,128.38,128.3,128.2,128.1,127.9,127.3,126.14,126.10,125.6,125.4,114.7,114.6,114.4,114.3,114.2,113.8,113.6,56.4,56.20,56.15,55.9,55.8,55.5,55.0,34.4,33.8,30.3,30.2,29.4.

[0221] Embodiment 27

[0222] Preparation of compound IIe, the reaction formula is as follows:

[0223]

[0224] The specific preparation method is:

[0225] The difference from Example 23 is that phenylboronic acid 4k (47.5 mg, 0.25 mmol, 5.0 equiv) is replaced by phenylboronic acid 4i (55.5 mg, 0.25 mmol, 5.0 equiv), to obtain 40.1 mg of compound IIe with a yield of 81% and an ee value of 95%.

[0226] 1 HNMR(500MHz,Chloroform-d)δ7.88–7.83(m,1H),7.71–7.69(m,1H),7.53(s,1H),7.51–7.48(m,2H),7.47 (d,J=8.0Hz,1H),7.10(s,1H),7.04(d,J=8.1Hz,2H),7.00(s,1H),6.92(d,J=8.4Hz,1H),6.83(d,J=8.2Hz, 2H),6.75(s,2H),6.74(s,1H),6.73(s,1H),6.57(s,1H),6.53(s,1H),5.98(s,1H),5.68(s,1H),3.99–3.80 (m,9H),3.80–3.65(m,10H),3.59(s,3H),3.51(s,3H),3.41(s,3H),3.38(s,3H),3.28(s,3H),2.94(s,3H). 13 CNMR(126MHz,Chloroform-d)δ158.4,151.3,151.2,151.10,151.05,150.9,150.8,150.6,14 0.3,140.1,140.0,136.8,136.7,134.8,132.5,132.3,130.5,128.8,128.7,128.5,128.1,12 8.0,127.73,127.70,127.5,126.1,125.7,114.6,114.438,114.3,114.3,114.0,113.7,113.5,56.3,56.2,56.14,56.11,55.81,55.75,55.73,55.4,55.0,34.1,33.7,30.3,30.1,29.41.

[0227] Embodiment 28

[0228] Preparation of compound IIf, the reaction formula is as follows:

[0229]

[0230] The specific preparation method is:

[0231] The difference from Example 23 is that phenylboronic acid 4k (47.5 mg, 0.25 mmol, 5.0 equiv) is replaced by phenylboronic acid 4m (41.7 mg, 0.25 mmol, 5.0 equiv), and 32.7 mg of compound IIf can be obtained with a yield of 71% and an ee value of 95%.

[0232] 1 HNMR(500MHz,Chloroform-d)δ7.89(d,J=8.2Hz,2H),7.09(d,J=7.6Hz,3H),6.86(d,J= 8.8Hz,4H),6.80(d,J=7.4Hz,2H),6.76(s,1H),6.68(s,1H),6.65(s,1H),6.54(s,1H), 6.51(s,1H),6.08(s,1H),5.86(s,1H),3.96–3.84(m,7H),3.79–3.71(m,8H),3.69–3.6 6(m,4H),3.62(s,3H),3.57(s,3H),3.46(s,3H),3.37(s,3H),3.35(s,3H),3.28(s,3H). 13 CNMR(126MHz,C hloroform-d)δ158.7,151.3,151.219,151.14,151.11,150.9,150.7,146.6,141.1,13 8.3,137.3,136.7,134.2,132.5,131.2,130.4,129.8,129.3,129.2,128.8,128.74,128 .71,128.6,127.9,127.5,123.1,114.6,114.5,114.4,114.2,114.14,114.07,113.9,113.7,56.22,56.18,56.1,56.0,55.71,55.68,55.5,55.4,33.8,33.7,30.5,29.9,29.8.

[0233] Embodiment 29

[0234] Preparation of compound IIIa (corresponding to R in structural formula II1 For -CH3), the reaction formula is as follows:

[0235]

[0236] The specific preparation method is:

[0237] Compound VIII (63.8 mg, 0.05 mmol, 1.0 equiv), phenylboronic acid 4 g (49.5 mg, 0.25 mmol, 5.0 equiv), Pd(OAc)2 (2.2 mg, 20 mol%), Na3PO4 (81.9 mg, 0.5 mmol, 10.0 equiv), L22 (10.6 mg, 40 mol%), and 1,4-dioxane (2.0 mL) were added to a 100 mL Shrek tube equipped with a stirrer, and stirred at 80 ° C for 24 h under a nitrogen atmosphere. After cooling to room temperature, the mixture was dried by spin drying, and the residue was separated by column chromatography on 230-400 mesh silica gel with petroleum ether: diethyl ether = 10:1 to obtain 50.0 mg of compound IIIa with a yield of 70% and an ee value of 95%.

[0238] 1 HNMR(500MHz,Chloroform-d)δ7.61(d,J=7.5Hz,4H),7.52(d,J=8.0Hz,4H),7.47(t,J=7. 6Hz,4H),7.37(t,J=7.4Hz,2H),7.28(d,J=8.0Hz,4H),7.21(s,2H),6.76(s,4H),6.65(s,2 H),6.60(s,2H),6.06(s,2H),4.04(d,J=14.3Hz,2H),3.87–3.79(m,18H),3.76–3.71(m,6 H),3.70–3.63(m,2H),3.59–3.51(m,4H),1.36–1.22(m,20H),1.14(m,J=7.0,3.7Hz,10H). 13 C NMR(126MHz,Chloroform-d)δ150.63,150.59,150.57,150.4,150.3,141.5,141.1,140.4,139.3,136.2,132.6,130.2,128.9,128.1,12 8.0,127.8,127.4,127.1,126.6,115.7,115.4,115.2,114.57,64.3,64.13,64.06,63.99,63.9,33.8,31.12,30.95,15.4,15.19,15.17.

[0239] Experimental Testing

[0240] The compound Ig prepared in Example 10 was subjected to X-ray single crystal diffraction test. Figure 4 As shown, the obtained X-ray single crystal diffraction structure proves that the structure of compound Ig is correct and its absolute configuration is pS.

[0241] The compounds I prepared in Example 6, Example 7, Example 10, Example 11, Example 12 and Example 13 were tested for UV absorption and fluorescence emission. The test results are as follows: Figure 5 and Figure 6 As shown, it is shown that the bifunctionalized chiral pillar aromatics prepared by asymmetric catalytic Suzuki coupling reaction have excellent luminescence properties.

[0242] Therefore, the present invention adopts the above-mentioned functionalized planar chiral columnar aromatics and its preparation method and application to obtain a chiral columnar aromatics derivative with high yield, high ee value, high optical activity, excellent fluorescence emission performance and a large electron-rich cavity, which can be used as a chiral luminescent material, a chiral catalyst carrier, etc.

[0243] Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention rather than to limit it. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that they can still modify or replace the technical solution of the present invention with equivalents, and these modifications or equivalent replacements cannot cause the modified technical solution to deviate from the spirit and scope of the technical solution of the present invention.

Claims

1. A functionalized planar chiral pillar aromatic hydrocarbon, characterized in that: Including compound I, compound II, compound III, compound IV, compound V and compound VI, and also including stereoisomers of compound I, compound II, compound III, compound IV, compound V or compound VI; The structural formulas of the compound I, the compound II, the compound III, the compound IV, the compound V and the compound VI are respectively as follows: Among them, R 1 Selected from C 1-10 Alkyl, C 3-10 Cycloalkyl, C 5-15 Aryl, benzyl, the C 1-10 The alkyl group is optionally inserted by one or more groups selected from oxygen atoms, carbonyl groups, and the C 3-10 Cycloalkyl, the C 5-15 The aryl group and the benzyl group are each independently optionally substituted with one or more C 1-5 Alkyl substitution; R 2 and R 3 Different and each independently selected from C 5-15 Aryl, C 5-15 Heteroaryl, the R 2 Optionally one or more independently selected from R a Substituents, said R 3 Optionally one or more independently selected from R m substituted by a substituent; Among them, the R a , the R m Each independently selected from C 1-10 Alkyl, C 1-10 Alkoxy, C 5-15 Aryloxy, C 6-16 Arylalkoxy, C 2-10 Alkenyl, C 2-10 Alkynyl, C 3-10 Cycloalkyl, C 5-15 Aryl, C 5-15 heteroaryl, halogen, trifluoromethyl, nitro, cyano, the R a Optionally one or more independently selected from R b Substituents, said R m Optionally one or more independently selected from R n Substituents are substituted; Among them, the R b , the R n Each independently selected from C 1-10 Alkyl, C 1-10 Alkoxy, C 2-10 Alkenyl, C 2-10 Alkynyl, C 3-10 Cycloalkyl, C 5-15 Aryl, C 5-15 Heteroaryl, halogen, trifluoromethyl, nitro, cyano.

2. The functionalized planar chiral pillar aromatic hydrocarbon according to claim 1, characterized in that: The R 1 Selected from methyl, ethyl, propyl, butyl, 3-carbomethyl, cyclohexyl, benzyl, naphthylmethyl, anthracenemethyl and phenanthrylmethyl.

3. The functionalized planar chiral pillar aromatic hydrocarbon and its preparation method and application according to claim 2, characterized in that: The R 2 , the R 3 Each is independently selected from phenyl, naphthyl, anthracenyl, phenanthrenyl, pyrenyl; The R a , R m Each is independently selected from methyl, methoxy, ethyl, propyl, butyl, tert-butyl, phenyl, benzyloxy, fluoro, cyano, nitro, trifluoromethyl.

4. The functionalized planar chiral pillar aromatic hydrocarbon according to claim 2, characterized in that: The R 2 , the R 3 Each is independently selected from p-methoxyphenyl, p-ethoxyphenyl, p-methylphenyl, p-ethylphenyl, p-propylphenyl, p-tert-butylphenyl, p-benzylphenyl, p-nitrophenyl, p-fluorophenyl, p-trifluoromethylphenyl, p-cyanophenyl, p-nitrophenyl, naphthyl, anthracenyl, phenanthrenyl, pyrenyl, diphenylanthryl and tetraphenylethylene.

5. A method for preparing a functionalized planar chiral pillar aromatic hydrocarbon according to any one of claims 1 to 4, characterized in that: The following steps are involved: According to a certain ratio, an organic boron compound, a palladium catalyst, a chiral ligand, a base and pillar[n]arene are added to a solvent for an oxygen-free heating reaction, and after the reaction is completed, a post-treatment is performed to obtain a chiral pillar[n]arene derivative; Wherein, when n=5, the pillar[n]arene is compound VII, and its structural formula is as follows: When n=6, the pillar[n]arene is compound VIII, and its structural formula is as follows: Among them, R 1 Selected from C 1-10 Alkyl, C 3-10 Cycloalkyl, C 5-15 Aryl, benzyl, the C 1-10 The alkyl group is optionally inserted by one or more groups selected from oxygen atoms, carbonyl groups, and the C 3-10 Cycloalkyl, the C 5-15 The aryl group and the benzyl group are each independently optionally substituted with one or more C 1-5 Alkyl substitution.

6. The method for preparing a functionalized planar chiral pillar aromatic hydrocarbon according to claim 5, characterized in that: The organic boronic acid compound is one of 4-methoxyphenylboric acid, 4-methylphenylboric acid, 4-ethylphenylboric acid, 4-propylphenylboric acid, 4-tert-butylphenylboric acid, 4-fluorophenylboric acid, 4-nitrobenzeneboric acid, 4-trifluoromethylphenylboric acid, 4-cyanophenylboric acid, 4-phenylphenylboric acid, 4-benzyloxyphenylboric acid, naphthylphenylboric acid, anthracenylphenylboric acid, phenanthrenylphenylboric acid, pyrenylphenylboric acid, 9,10-diphenylanthrylboric acid, p-triphenylvinylphenylboric acid, and p-terpyridylphenylboric acid; The molar ratio of the pillar[n]arene to the organic boronic acid compound is greater than 1:

2.

7. The method for preparing a functionalized planar chiral pillar aromatic hydrocarbon according to claim 5, characterized in that: The palladium catalyst comprises an organic palladium catalyst, and the organic palladium catalyst is one or more of Pd(PPh3)4, Pd2(dba)3, and Pd(OAc)2; The chiral ligand includes a chiral phosphimide ligand; The base is one or more of alkali metal phosphates, alkali metal carbonates, alkali metal acetates, organic amines, and alkali metal alkylsilanols; The solvent is an organic solvent or an aqueous solution of an organic solvent.

8. The method for preparing a functionalized planar chiral pillar aromatic hydrocarbon according to claim 7, characterized in that: The palladium catalyst is Pd(OAc)2; The chiral phosphimide ligand is L22 or one of the stereoisomers of L22, and the structural formula of L22 is as follows: The alkali is one or both of Na3PO4 and K3PO4.

9. The method for preparing a functionalized planar chiral pillar aromatic hydrocarbon according to claim 7, characterized in that: The organic solvent is one or more of toluene, 1,4-dioxane, N,N-dimethylformamide, N,N-dimethylacetamide, and tetrahydrofuran, and the volume ratio of the organic solvent to water in the aqueous solution of the organic solvent is greater than 4.

10. Use of a chiral pillararene derivative prepared by the method for preparing a functionalized planar chiral pillararene according to any one of claims 5 to 9 in a chiral luminescent material or a chiral catalyst carrier.

Images