阅读说明：本技术 一种拆分手性化合物的方法 (Method for splitting chiral compound ) 是由 杨晓瑜 刘炜 于 2020-05-25 设计创作，主要内容包括：本发明涉及有机化学领域,特别是涉及一种拆分手性化合物的方法。本发明所提供的拆分手性化合物的方法,包括：将消旋的式A化合物在催化剂存在的条件下与偶氮二甲酸酯进行加成反应,以提供S构型的式A化合物和式C化合物。本发明所提供的拆分手性化合物的方法,以手性磷酸作为催化剂,具有良好的催化效果、且同时具有很广的底物适用性,无论产物和回收原料都能以优异的对映选择性得到,动力学拆分的选择性系数可以达到371,并对于各种N-单取代以及N-无取代联萘二胺、H8-联萘二胺以及联苯二胺都具有优异的动力学拆分效果。(The invention relates to the field of organic chemistry, in particular to a method for splitting a chiral compound. The method for resolving the chiral compound provided by the invention comprises the following steps: and (3) carrying out addition reaction on the racemic compound of the formula A and the azodicarboxylate in the presence of a catalyst to provide the compound of the formula A and the compound of the formula C in S configuration. The method for splitting the chiral compound provided by the invention takes chiral phosphoric acid as a catalyst, has good catalytic effect and wide substrate applicability, can be obtained by excellent enantioselectivity no matter the product and the recovered raw material, has a selectivity coefficient of kinetic resolution up to 371, and has excellent kinetic resolution effect on various N-monosubstituted and N-unsubstituted binaphthyl diamine, H8-binaphthyl diamine and biphenyldiamine.)

1. A method of resolving a chiral compound comprising:

performing an addition reaction on the racemic compound of the formula A and the azodicarbonic ester in the presence of a catalyst to provide a compound of the formula A and a compound of the formula C in an S configuration, wherein the reaction equation is as follows:

wherein R is¹Selected from hydrogen, aryl, arylalkyl, -C (O) O-R ', -C (O) -R', -SO₂-R ' ", wherein R ' is selected from C1-C4 alkyl, arylalkyl, R" is selected from C1-C4 alkyl, aryl, arylalkyl, R ' "is selected from C1-C4 alkyl, aryl;

R²、R³each independently selected from hydrogen, C1-C4 alkyl, aryl, -C ≡ C-SiR^x ₃Halogen, C1-C4 alkoxy, wherein R^xSelected from C1-C3 alkyl;

R⁴、R⁵each independently selected from C1-C4 alkyl, arylalkyl;

the catalyst is selected from chiral phosphoric acid catalysts.

2. A process for resolving chiral compounds as claimed in claim 1, wherein R is⁴、R⁵Are the same group.

3. A process for resolving chiral compounds as claimed in claim 1, wherein R is¹Selected from hydrogen, benzyl, -C (O) O-R ', -C (O) -R', -SO₂-R ' ", wherein R ' is selected from tert-butyl, benzyl, R" is selected from phenyl, R ' "is selected from p-tolyl;

R²、R³each independently selected from hydrogen, C1-C3 alkyl, phenyl, -C ≡ C-SiMe₃Br, C1-C3 alkoxy;

R⁴、R⁵each independently selected from benzyl.

4. A process for resolving a chiral compound as claimed in claim 1, wherein said compound of formula a is selected from compounds having one of the following chemical structures:

5. the method for resolving chiral compounds of claim 1, wherein said chiral phosphoric acid catalyst isAn acid catalyst having a SPINOL backbone, a BINOL backbone, or H8-BINOL backbone.

6. The method of claim 5, wherein the chiral phosphoric acid catalyst is selected from the group consisting of compounds having one of the following chemical structures:

wherein R is⁶And R⁷Each independently selected from 2,4,6- (iPr)₃C₆H₂；

R⁸And R⁹Each independently selected from 2,4,6- (iPr)₃C₆H₂、Ph、1-Naphthyl、2-Naphthyl、9-Anthracenyl、2,4,6-(Me)₃C₆H₂、2,4,6-(Cy)₃C₆H₂；

R¹⁰And R¹¹Each independently selected from 2,4,6- (iPr)₃C₆H₂。

7. A process for resolving chiral compounds as claimed in claim 1, wherein the addition reaction is carried out in the presence of a solvent, preferably wherein the solvent is selected from the group consisting of aprotic solvents;

and/or, in the addition reaction, the molar ratio of the compound of the formula A to the azodicarboxylic acid ester is 1: 0.5-1, preferably, the molar ratio of the compound of the formula A to the azodicarboxylic acid ester is 1: 0.6-1: 0.7;

and/or, the addition reaction is carried out under anhydrous conditions;

and/or the reaction temperature of the addition reaction is-80 ℃ to-20 ℃, preferably, the reaction temperature of the addition reaction is-60 ℃ to-40 ℃;

and/or, the post-treatment of the addition reaction comprises: quenching, removing the solvent, and purifying to provide the compound of formula A and the compound of formula C in S configuration.

8. A method of resolving a chiral compound as claimed in claim 1, further comprising: providing a compound of formula a in R configuration by a compound of formula C, the reaction equation is as follows:

9. the method for resolving chiral compounds of claim 8, wherein the compound of formula a in R configuration is provided by a compound of formula C, in particular: the compound of formula C is reductively hydrogenated to provide the compound of formula a in the R configuration.

10. The method for resolving chiral compounds as claimed in claim 1, wherein the reductive hydrogenation reaction is performed in the presence of a catalyst, preferably, the reductive hydrogenation reaction is performed by using a catalyst selected from one or more of nickel-based catalyst and palladium-carbon catalyst;

and/or, the reductive hydrogenation reaction is carried out in the presence of a solvent, preferably, the solvent in the reductive hydrogenation reaction is selected from protic solvents;

and/or the reaction temperature of the reduction hydrogenation reaction is 20-100 ℃, preferably, the reaction temperature of the reduction hydrogenation reaction is 20-50 ℃.

Technical Field

The invention relates to the field of organic chemistry, in particular to a method for splitting a chiral compound.

Background

Chiral 1,1' -bi-2-naphthylamine and derivatives thereof are extremely important chiral compounds, which are widely used for synthesis of various chiral organic catalysts and chiral ligands, and are also used for chiral materials such as chiral separation stationary phases, chiral liquid crystal materials, chiral molecular switches and the like. However, asymmetric synthesis of such chiral compounds still relies on chemical resolution with equivalent chiral resolving agents, which is inefficient (J.org.chem.1985,50, 4345-4349). And a method for realizing chiral binaphthyl diamine by using a more efficient asymmetric catalysis method is still lacked. The List and Kurti project groups reported that asymmetric rearrangement of 2,2' -hydrazinonaphthalene to binaphthyl diamine was achieved using an organocatalytic [3,3] -diazacope rearrangement, but this method was only applicable to symmetric binaphthylamine substrates, while the starting material required a multi-step synthesis and was unstable (Angew. chem. int. Ed.2013,52, 9293-9295; J.am. chem. Soc.2013,135, 7414-7417). The Tan topic group reports asymmetric addition reaction of 2-naphthylamine and 2-azonaphthalene under catalysis of chiral Lewis acid, and various chiral 1,1' -bi-2-naphthylamine products (nat. Catal.2019,2, 314-. Another method for synthesizing binaphthyl diamine by asymmetric catalysis is kinetic resolution, and Tan subject group reports that the kinetic resolution is realized by using asymmetric reductive amination reaction of racemic binaphthyl diamine and aldehyde to synthesize chiral binaphthyl diamine; however, the binaphthyl diamine as the raw material in the method needs protection, and additional protection and deprotection operations are needed in the synthesis process (Angew. chem. int. Ed.2014,53, 3684-.

Therefore, the development of a more direct, efficient and economical asymmetric catalytic method for synthesizing the chiral binaphthyl diamine still has important synthetic significance.

Disclosure of Invention

In view of the above-mentioned drawbacks of the prior art, it is an object of the present invention to provide a method for resolving chiral compounds, which solves the problems of the prior art.

To achieve the above and other related objects, the present invention provides, in one aspect, a method for resolving a chiral compound, comprising:

performing an addition reaction on the racemic compound of the formula A and the azodicarbonic ester in the presence of a catalyst to provide a compound of the formula A and a compound of the formula C in an S configuration, wherein the reaction equation is as follows:

wherein R is¹Selected from hydrogen, aryl, arylalkyl, -C (O) O-R ', -C (O) -R', -SO₂-R ' ", wherein R ' is selected from C1-C4 alkyl, arylalkyl, R" is selected from C1-C4 alkyl, aryl, arylalkyl, R ' "is selected from C1-C4 alkyl, aryl;

R²、R³each independently selected from hydrogen, C1-C4 alkyl, aryl, -C ≡ C-SiR^x ₃Halogen, C1-C4 alkoxy, wherein R^xSelected from C1-C3 alkyl;

R⁴、R⁵each independently selected from C1-C4 alkyl, arylalkyl;

the catalyst is selected from chiral phosphoric acid catalysts.

In some embodiments of the invention, R⁴、R⁵Are the same group.

In some embodiments of the invention, R¹Selected from hydrogen, benzyl, -C (O) O-R ', -C (O) -R', -SO₂-R ' ", wherein R ' is selected from tert-butyl, benzyl, R" is selected from phenyl, R ' "is selected from p-tolyl;

R²、R³each independently selected from hydrogen, C1-C3 alkyl, phenyl, -C ≡ C-SiMe₃Br, C1-C3 alkoxy;

R⁴、R⁵each independently selected from benzyl.

In some embodiments of the invention, the compound of formula a is selected from compounds having one of the following chemical structures:

in some embodiments of the invention, the chiral phosphoric acid catalyst isAn acid catalyst having a SPINOL backbone, a BINOL backbone, or H8-BINOL backbone.

In some embodiments of the invention, the chiral phosphoric acid catalyst is selected from compounds having one of the following chemical structures:

wherein R is⁶And R⁷Each independently selected from 2,4,6- (iPr)₃C₆H₂；

R⁸And R⁹Each independently selected from 2,4,6- (iPr)₃C₆H₂、Ph、1-Naphthyl、2-Naphthyl、9-Anthracenyl、2,4,6-(Me)₃C₆H₂、2,4,6-(Cy)₃C₆H₂；

R¹⁰And R¹¹Each independently selected from 2,4,6- (iPr)₃C₆H₂。

In some embodiments of the invention, the addition reaction is carried out in the presence of a solvent, preferably, the solvent is selected from aprotic solvents.

In some embodiments of the invention, the molar ratio of the compound of formula a to the azodicarboxylate in the addition reaction is 1: 0.5-1: 1; preferably, the molar ratio of the compound of formula a to the azodicarboxylate is 1: 0.6-1: 0.7

In some embodiments of the invention, the addition reaction is carried out under anhydrous conditions.

In some embodiments of the invention, the reaction temperature of the addition reaction is-80 ℃ to-20 ℃, preferably the reaction temperature of the addition reaction is-60 ℃ to-40 ℃.

In some embodiments of the invention, the post-treatment of the addition reaction comprises: quenching, removing the solvent, and purifying to provide the compound of formula A and the compound of formula C in S configuration.

In some embodiments of the invention, the method further comprises: providing a compound of formula a in R configuration by a compound of formula C, the reaction equation is as follows:

in some embodiments of the invention, the method of providing a compound of formula a in the R configuration by a compound of formula C is specifically: the compound of formula C is reductively hydrogenated to provide the compound of formula a in the R configuration.

In some embodiments of the present invention, the reductive hydrogenation reaction is performed in the presence of a catalyst, and preferably, the catalyst is selected from one or more of a nickel-based catalyst and a palladium-carbon catalyst.

In some embodiments of the present invention, the reductive hydrogenation is carried out in the presence of a solvent, preferably, the solvent is selected from protic solvents.

In some embodiments of the present invention, the reaction temperature of the reductive hydrogenation reaction is 20 ℃ to 100 ℃, and preferably, the reaction temperature of the reductive hydrogenation reaction is 20 ℃ to 50 ℃.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments, and other advantages and effects of the present invention will be apparent to those skilled in the art from the disclosure of the present specification.

The inventor of the invention unexpectedly discovers a method for synthesizing chiral binaphthyl diamine compounds and biphenyl diamine compounds by catalytic kinetic resolution through a large amount of practical researches, and the method has the advantages of wide substrate applicability, high catalytic efficiency, simple operation, low cost, environmental friendliness and the like, thereby completing the invention.

The invention provides a method for resolving chiral compounds, which comprises the following steps:

performing an addition reaction on the racemic compound of the formula A and the azodicarbonic ester in the presence of a catalyst to provide a compound of the formula A and a compound of the formula C in an S configuration, wherein the reaction equation is as follows:

wherein R is¹Selected from hydrogen, aryl, arylalkyl, -C (O) O-R ', -C (O) -R', -SO₂-R ' ", wherein R ' is selected from C1-C4 alkyl, arylalkyl, R" is selected from C1-C4 alkyl, aryl, arylalkyl, R ' "is selected from C1-C4 alkyl, aryl;

R²、R³each independently selected from hydrogen, C1-C4 alkyl, aryl, -C ≡ C-SiR^x ₃Halogen, C1-C4 alkoxy, wherein R^xSelected from C1-C3 alkyl;

R⁴、R⁵each independently selected from C1-C4 alkyl, arylalkyl;

the catalyst is selected from chiral phosphoric acid catalysts. In the above reaction equation, R²The substituted aromatic ring may be a naphthalene ring or a benzene ring comprising two methyl substituents. When R is²When the substituted aromatic ring is a naphthalene ring, R²The substituted position of (A) is not limited to C5, C6, C7 and C8 substitution of naphthalene ring, but C3, C4, C5, C6, C7 and C8 substitution can be carried out, and when R is R, R is substituted²When the substituted aromatic ring is a benzene ring comprising two methyl substituents, R²The substitution position of (b) may be on the benzene ring or on the methyl substituent of the benzene ring. Corresponding to, R³The substituted aromatic ring may be a naphthalene ring or a benzene ring comprising two methyl substituents. When R is³When the substituted aromatic ring is a naphthalene ring, R³The substituted position of (A) is not limited to C5, C6, C7 and C8 substitution of naphthalene ring, but C3, C4, C5, C6, C7 and C8 substitution can be carried out, and when R is R, R is substituted³When the substituted aromatic ring is a benzene ring comprising two methyl substituents, R²The substitution position of (b) may be on the benzene ring or on the methyl substituent of the benzene ring.

As used herein, "alkyl" generally refers to a saturated aliphatic group, which may be straight-chain or branched. For example, C1-C4 alkyl generally refers to alkyl groups of 1,2, 3, 4 carbon atoms. Specific alkyl groups may be, for example, methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, sec-butyl, tert-butyl, and the like.

In the present application, "alkynyl" generally refers to an unsaturated aliphatic group and includes a C ≡ C bond (carbon-carbon triple bond, acetylene bond), which may be linear or branched. For example, C2-C6 alkynyl generally refers to alkynyl groups of 2,3, 4,5, 6 carbon atoms. Specific alkynyl groups can be, for example, ethynyl, propynyl, butynyl, pentynyl, hexynyl, and the like.

In the present application, "aryl" generally refers to a group having a ring system of at least one aromatic ring and no hetero atom, and the aryl group may be substituted or unsubstituted, for example, the substituent may be an alkyl group or the like. Specific aryl groups may be, for example, phenyl, tolyl, and the like.

As used herein, "arylalkyl" generally includes a straight or branched chain alkyl group (as defined above) bonded to an aryl group. Specific arylalkyl groups can be, for example, benzyl and the like.

In one embodiment of the present invention, R⁴、R⁵Are the same group.

In one embodiment of the present invention, R¹Selected from hydrogen, benzyl, -C (O) O-R ', -C (O) -R', -SO₂-R ' ", wherein R ' is selected from tert-butyl, benzyl, R" is selected from phenyl and R ' "is selected from p-tolyl.

In one embodiment of the present invention, R²、R³Each independently selected from hydrogen, C1-C3 alkyl, phenyl, -C ≡ C-SiMe₃Br, C1-C3 alkoxy.

In one embodiment of the present invention, R⁴、R⁵Each independently selected from benzyl.

In a more specific embodiment of the invention, the compound of formula a is selected from compounds having one of the following chemical structures:

in the above addition reaction, the chiral phosphoric acid catalyst is usuallyAcid catalysts, this class of chiral phosphoric acid catalysts can typically have 2,2',3,3' -tetrahydro-1, 1' -spirobi [ indene](SPINOL) skeleton, BINOL skeleton, or H8-BINOL skeleton, etc. Specifically, the chiral phosphoric acid catalyst may be selected from, but is not limited to, compounds having one of the following chemical structures:

wherein R is⁶And R⁷Each independently selected from 2,4,6- (iPr)₃C₆H₂；

R⁸And R⁹Each independently selected from 2,4,6- (iPr)₃C₆H₂、Ph、1-Naphthyl、2-Naphthyl、9-Anthracenyl、2,4,6-(Me)₃C₆H₂、2,4,6-(Cy)₃C₆H₂；

R¹⁰And R¹¹Each independently selected from 2,4,6- (iPr)₃C₆H₂. The chiral phosphoric acid catalyst may generally be used in catalytic amounts, for example, the molar ratio of the compound of formula a to the chiral phosphoric acid catalyst may be 1: 0.3-0.01, 1: 0.3-0.2, 1: 0.2-0.1, 1: 0.1-0.06, 1: 0.06-0.04, 1: 0.04-0.02, or 1:0.02 to 0.01. In one embodiment of the present invention, the molar ratio of the compound of formula a to the chiral phosphoric acid catalyst may be 1:0.1 to 0.02.

In the above addition reaction, the compound of formula a may be generally present in a substantially equal amount or in an excess amount with respect to the diazodicarboxylate in the reaction system, so that the conversion rate of the reaction can be ensured and the reaction can be sufficiently forward, for example, the molar ratio of the compound of formula a to the diazodicarboxylate in the addition reaction may be 1: 0.5-1, 1: 0.5-0.6, 1: 0.6-0.7, 1: 0.7-0.8, 1: 0.8 to 0.9, or 1: 0.9 to 1. In one embodiment of the present invention, the molar ratio of the compound of formula a to the azodicarboxylate may be 1: 0.6 to 0.7.

In the addition reaction, the reaction may be carried out in the presence of a solvent, and the solvent used in the addition reaction may be an aprotic solvent and may be a good solvent for the reaction system. For example, the solvent used in the addition reaction may be specifically a haloalkane solvent, an aromatic solvent, or the like, and in one embodiment of the present invention, the solvent used in the addition reaction may be one or a combination of more of chloroform, dichloromethane, toluene, benzene, or the like. For another example, the amount of the solvent used in the addition reaction can be referred to the concentration of the compound of formula A in the system, for example, the concentration of the compound of formula A in the reaction system can be 0.3 to 0.005mmol/mL, 0.3 to 0.2mmol/mL, 0.2 to 0.1mmol/mL, 0.1 to 0.05mmol/mL, 0.05 to 0.03mmol/mL, 0.03 to 0.02mmol/mL, 0.02 to 0.0125mmol/mL, or 0.0125 to 0.005mmol/mL, and in one embodiment of the present invention, the concentration of the compound of formula A in the reaction system can be 0.1 to 0.0125 mmol/mL.

In the above addition reaction, the reaction is generally required to be carried out under anhydrous conditions, mainly due to the fact that hydrogen bonds are formed between the catalyst and the compound of formula a in the reaction system, so that the compound a is activated and the stereoselectivity of the reaction is controlled.

In the above addition reaction, the reaction is usually carried out at a low temperature, for example, the reaction temperature of the addition reaction may be from-80 ℃ to-20 ℃, from-80 ℃ to-60 ℃, from-60 ℃ to-40 ℃, or from-40 ℃ to-20 ℃, and in one embodiment of the present invention, the reaction temperature of the addition reaction may be from-40 ℃ to-60 ℃. The reaction time can be adjusted by those skilled in the art according to the reaction progress, for example, the reaction progress of the addition reaction can be judged by TLC, chromatography, etc., and for example, the reaction time of the addition reaction can be 4 to 240 hours, 4 to 8 hours, 8 to 12 hours, 12 to 24 hours, 24 to 48 hours, 48 to 72 hours, 72 to 120 hours, 120 to 180 hours, 180 to 240 hours, and in an embodiment of the present invention, the reaction time of the addition reaction can be 12 to 120 hours.

In the above addition reaction, the skilled person can select a suitable method to post-treat the product of the addition reaction, for example, the post-treatment of the addition reaction may include: quenching, removing the solvent, and purifying to provide the compound of formula A and the compound of formula C in S configuration. Suitable quenching methods should be known to those skilled in the art, and for example, an appropriate amount of a base (e.g., triethylamine, etc.) may be added to the reaction system. Suitable purification methods in addition reactions should be known to those skilled in the art, and may be, for example, column chromatography and the like.

The method for resolving the chiral compound provided by the invention can further comprise the following steps: providing a compound of formula a in R configuration by a compound of formula C, the reaction equation is as follows:

the person skilled in the art can select suitable methods to provide compounds of formula a in the R configuration by compounds of formula C, for example, in particular as follows: the compound of formula C is reductively hydrogenated to provide a compound of formula A in the R configuration, the reductive hydrogenation reaction generally being carried out in H₂Under the provided reducing atmosphere.

In the above-mentioned reductive hydrogenation reaction, the reaction may be usually carried out in the presence of a catalyst. The type and amount of suitable catalyst for the reductive hydrogenation reaction should be known to those skilled in the art, for example, the catalyst in the reductive hydrogenation reaction may be one or more of a nickel-based catalyst (e.g., raney nickel, etc.), a palladium-on-carbon catalyst (e.g., palladium-on-carbon, etc.), and the like. For another example, the catalyst used in the reductive hydrogenation reaction may be a catalytic amount, the molar ratio of the compound of formula C to the catalyst may be 1: 0.02-0.5, 1: 0.02-0.05, 1: 0.05-0.1, 1: 0.1-0.2, 1: 0.2-0.3, or 1: 0.3-0.5, and in one embodiment of the present invention, the molar ratio of the compound of formula C to the catalyst may be 1: 0.05-0.1.

In the above-mentioned reductive hydrogenation reaction, the reaction may be usually carried out in the presence of a solvent. The kind and amount of suitable solvent for the reductive hydrogenation reaction should be known to those skilled in the art, and preferably, the solvent used in the reductive hydrogenation reaction may be selected from protic solvents and the like, and more specifically, may be methanol and the like; for another example, the amount of the solvent used in the reductive hydrogenation reaction can be referred to the concentration of the compound of formula C in the reaction system, for example, the concentration of the compound of formula C in the reaction system can be 0.01 to 0.5mmol/mL, 0.01 to 0.025mmol/mL, 0.025 to 0.05mmol/mL, 0.05 to 0.1mmol/mL, 0.1 to 0.2mmol/mL, 0.2 to 0.3mmol/mL, or 0.3 to 0.5mmol/mL, and in one embodiment of the present invention, the concentration of the compound of formula C in the reaction system can be 0.025mmol/mL to 0.1 mmol/mL.

In the above-mentioned reductive hydrogenation reaction, the reaction is usually performed at room temperature or under heating, for example, the reaction temperature of the reductive hydrogenation reaction may be from room temperature to the boiling point of the solvent, and more specifically may be from 20 to 100 ℃, from 20 to 30 ℃, from 30to 40 ℃, from 40 to 50 ℃, from 50 to 60 ℃, from 60 to 80 ℃, or from 80 to 100 ℃, in an embodiment of the present invention, the reaction temperature of the reductive hydrogenation reaction may be from 20 to 50 ℃. The reaction time can be adjusted by those skilled in the art according to the reaction progress, for example, the reaction progress of the reductive hydrogenation reaction can be judged by TLC, chromatography, etc., and for example, the reaction time of the reductive hydrogenation reaction can be 4 to 144 hours, 4 to 8 hours, 8 to 12 hours, 12 to 24 hours, 24 to 48 hours, 48 to 72 hours, and 72 to 144 hours, and in an embodiment of the present invention, the reaction time of the reductive hydrogenation reaction can be 12 to 72 hours.

In the above-mentioned reductive hydrogenation reaction, a person skilled in the art can select a suitable method for post-treating the product of the reductive hydrogenation reaction, for example, the post-treatment of the reductive hydrogenation reaction may include: solid-liquid separation, solvent removal and purification to provide the compound of formula a in R configuration. Suitable purification methods in the reductive hydrogenation reaction should be known to those skilled in the art, and may be, for example, column chromatography and the like.

The method for splitting the chiral compound provided by the invention takes chiral phosphoric acid as a catalyst, has good catalytic effect and wide substrate applicability, can be obtained by excellent enantioselectivity no matter the product and the recovered raw material, has a selectivity coefficient of kinetic resolution up to 371, and has excellent kinetic resolution effect on various N-monosubstituted and unsubstituted binaphthyl diamine, H8-binaphthyl diamine and biphenyldiamine. In addition, the method provided by the application also has the advantages of easily available raw materials, simplicity in operation, low cost, environmental friendliness and the like, and each raw material can be obtained cheaply through a market approach or can be obtained through synthesis through simple steps, so that the method has a good industrialization prospect.

The invention of the present application is further illustrated by the following examples, which are not intended to limit the scope of the present application.

The instrument and experimental material information used in each example is as follows:

thin Layer Chromatography (TLC) used yellow sea HSGF254 silica gel plates.

The silica gel column chromatography is performed by using yellow sea HHGJ-300 silica gel (300-.

¹H NMR and¹³c NMR was characterized by Bruker 400MHz or 500MHz NMR spectrometer, and solvents were deuterated chloroform, deuterated acetone, and deuterated DMSO. Chemical shifts are in ppm and coupling constants are in Hz. In that¹In H NMR, chemical shifts are shown, s is a singlet, d is a doublet, t is a triplet, q is a quartet, p is a quintet, m is a multiplet, and br is a broad peak. In that¹³In C NMR, chemical shifts are indicated.

The enantiomeric excess values were determined by an Agilent 1260 chiral HPLC instrument and a xylonite IA, IB, IC chiral chromatography column.

High Resolution Mass Spectrometry (HRMS) Using an Agilent 6230TOF LC/MS Mass Spectroscopy apparatus, ion Source employs ESI⁺A source.

Infrared Spectroscopy Using ThermoFisher Scientific Nicolet iS7 Spectroscopy apparatus in cm^-1。