CN114478279B - Method for preparing chiral glycine derivative by asymmetric nickel catalytic hydrogenation - Google Patents

Abstract

The invention relates to the technical field of chemical engineering, and specifically relates to a method for preparing chiral glycine derivatives by asymmetric nickel catalytic hydrogenation of N-aryl-α-imide esters/amides. The method includes the following steps: in a solvent, a certain amount of Under hydrogen pressure and temperature, the N-aryl-α-imide ester/amide represented by the general formula (1) is hydrogenated into the chiral glycine derivative represented by the general formula (2) catalyzed by a nickel chiral catalyst; The structural formulas of the general formulas (1) and (2) are as follows: The reaction method of the present invention has mild conditions, is simple to operate, can achieve good reaction yield and reaction efficiency, and has good application effects.

Description

A method for preparing chiral glycine derivatives by asymmetric nickel catalytic hydrogenation

Technical field

The present invention relates to a method in the technical field of chemical engineering, in particular to a method for preparing chiral glycine derivatives, and in particular to an asymmetric nickel catalyzed hydrogenation method for preparing N-aryl-α-imide ester/amide. Glycine derivatives.

Background technique

Chiral glycine derivatives, especially chiral arylglycine derivatives, are useful skeletons found in natural products, active molecules and some drugs, and are also effective chiral intermediates in the synthesis of some natural compounds and drugs, for example, Ampicillin, cefadroxylin, clopidogrel, Elobixibat, HCV NS5B polymerase inhibitors and some steroidal compounds, etc. This is a basic class of structures that has a wide range of uses.

A literature search of the prior art found that the general methods for obtaining such chiral compounds are extraction, resolution, biological or synthetic methods from chiral raw materials, which have great limitations and are uneconomical.

At the same time, different attempts are also being made in chemical asymmetric synthesis methods. At present, they are mostly obtained by the asymmetric hydrogenation of imines catalyzed by precious metals. The expensive metal salts and heavy metal ions that are difficult to remove in the catalytic system greatly hinder the industrial application of this type of catalyst. The newly developed cheap transition metal catalysts can solve the above problems, but the catalytic activity needs to be improved urgently. According to literature research, there is currently only one report in 2020 on nickel-catalyzed cyclic N-sulfonylketimine ester to obtain chiral α-amino ester compounds, which achieved the highest conversion number of 50 and the highest enantioselectivity of 99% (Chem. Commun. 2020, 56, 4934-4937), and the nickel-catalyzed asymmetric hydrogenation of this type of acyclic ketimine ester substrate has not been reported.

In summary, chiral glycine derivatives are a widely used class of chiral substances. Developing green and efficient synthetic methods has become the focus of current research. So far, relevant reports using efficient nickel-catalyzed asymmetric hydrogenation of imines to synthesize such compounds with high yield and high enantioselectivity are still unsatisfactory. There is an urgent need to use efficient nickel catalysts to catalyze the synthesis of chiral glycine derivatives.

The publication number is CN109400508A, and the publication date is March 1, 2019. The Chinese patent document titled "Method for preparing macroscopically hindered chiral amines by asymmetric palladium-catalyzed hydrogen-form Z-form macrosterically hindered imine" discloses asymmetric palladium Method for preparing macroscopically hindered chiral amines by catalyzing hydrogen-formed Z-form macroscopically hindered imine. This patent is the result of the inventor's preliminary research on the use of precious metal palladium catalysts to solve the asymmetric hydrogenation of large sterically hindered imines connected to latent chiral carbon atoms to obtain large sterically hindered chiral amines. This reaction is not suitable for other small steric hindrances. Hydrogenation of imine groups, and the precious metal palladium has certain toxicity and is relatively expensive. This application solves the problem of asymmetric hydrogenation to synthesize another type of product - chiral glycine derivatives, and the cheap metal nickel catalyst used is almost non-toxic, cheap and easy to obtain, and is very suitable for industrial large-scale production.

Contents of the invention

In view of the above-mentioned deficiencies in the prior art, the present invention provides a reaction method for the preparation of asymmetric nickel catalytic hydrogenation. This preparation method uses a cheap transition metal asymmetric catalytic hydrogenation method to prepare chiral imines greenly, safely and efficiently. Glycine derivatives have the advantages of simple operation, high yield and high enantioselectivity.

The purpose of the present invention is achieved through the following technical solutions:

The invention provides a method for preparing chiral glycine derivatives by asymmetric nickel catalytic hydrogenation. The method includes the following steps: in a solvent, under a certain hydrogen pressure and temperature, catalyzed by a chiral catalyst of nickel, The N-aryl-α-imide ester/amide represented by formula (1) is hydrogenated into a chiral glycine derivative represented by general formula (2);

In general formulas (1) and (2), Ar represents an aryl group with or without a substituent;

R represents an aryl group with or without a substituent, or an alkyl group with 1 to 6 carbon atoms with or without a substituent;

X represents oxygen or nitrogen;

R ^' represents an alkyl group having 1 to 6 carbon atoms which may or may not have a substituent, or a benzyl group having 7 carbon atoms which may not have a substituent.

It should be noted that the method described in the present invention is particularly suitable for chiral arylglycine derivatives.

Preferably, the nickel chiral catalyst is complexed with nickel salts having different anions and chiral ligands.

Preferably, the nickel salt with different anions refers to a nickel salt whose anion is any one of chloride ion, bromide ion, acetate, trifluoroacetate, triflate and perchlorate.

Preferably, the chiral ligand refers to any ligand selected from L1 to L17, and the structural formula of the ligands L1 to L17 is as follows:

In L1-L6, Ar is selected from C ₆ H ₅ , 4-CH ₃ OC ₆ H ₄ , 4-CF ₃ C ₆ H ₄ or 3,5-di-tBu-4-MeOC ₆ H ₂ .

Preferably, the solvent refers to one or a mixture of one or more of non-polar solvents, polar solvents or protic solvents.

Preferably, the non-polar solvent is at least one of toluene, diethyl ether, and tetrahydrofuran; the polar solvent is at least one of dichloromethane, 1,2-dichloroethane, DMF, acetone, and acetonitrile. One; the protic solvent is at least one of methanol, ethanol, isopropyl alcohol, and trifluoroethanol.

More preferably, the solvent is at least one of toluene, dichloromethane, 1,2-dichloroethane, diethyl ether, tetrahydrofuran, methanol, ethanol, isopropanol, and trifluoroethanol.

Preferably, in the general formulas (1) and (2), R and R' each represent a group selected from the group consisting of methyl, ethyl, isopropyl, n-butyl, cyclohexyl, phenyl, and 2-methylphenyl. , 3-methylphenyl, 4-methylphenyl, 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2-fluorophenyl, 3-fluoro Phenyl, 4-fluorophenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 2-bromophenyl, 3-bromophenyl, 4-bromophenyl base, 2-iodophenyl, 3-iodophenyl, 4-iodophenyl, 1-naphthyl, 2-naphthyl, 3,4-dimethoxyphenyl, 3,4-dimethyl phenyl, 3,4-dichlorophenyl, 3,4-piperonylphenyl, 2,4-dimethylphenyl, 2,4-dimethoxyphenyl 2-furyl, five-membered Any one of cyclic groups and six-membered cyclic groups;

Or in the general formulas (1) and (2), the R and R ^' can be connected to form a ring respectively.

Preferably, the hydrogen pressure is 30 to 50 bar;

The molar ratio of the nickel chiral catalyst to the N-aryl-α-imide ester/amide represented by the general formula (1) is 1:20 to 10000;

The temperature is 0°C to 100°C, and the hydrogenation time is 6 to 72 hours.

Through experimental testing, under the conditions of using phosphine ligand L7, nickel acetate tetrahydrate, 30bar hydrogen, and 50°C for 24 hours, the imide ester substrates with different substituents have good adaptability and can obtain 81-99% yield and Efficient preparation of chiral glycine derivatives with 90%-98% enantioselectivity.

Compared with the prior art, the present invention has the following beneficial effects:

For the first time, the present invention uses a cheap transition metal asymmetric catalytic hydrogenation method to efficiently prepare chiral glycine derivatives of N-aryl-α-imide esters/amides. The reaction method has mild conditions, is easy to operate, and can achieve good reaction yield. rate and reaction efficiency, and has good application effects.

Detailed ways

The present invention will be described in detail below with reference to specific embodiments. The following examples will help those skilled in the art to further understand the present invention, but do not limit the present invention in any form. It should be noted that, for those of ordinary skill in the art, several changes and improvements can be made without departing from the concept of the present invention. These all belong to the protection scope of the present invention.

The method for preparing chiral glycine derivatives by asymmetric nickel catalytic hydrogenation of the present invention can be expressed by the following reaction formula:

In the above reaction formula, general formula (1) represents N-aryl-α-imide ester/amide, and general formula (2) represents a chiral glycine derivative.

In the general formulas (1) and (2), Ar represents an aryl group with or without a substituent; R represents an aryl group with or without a substituent, and An alkyl group with a substituent of 1 to 6 carbon atoms; Substituted or multi-substituted aryl or naphthalene such as fluoromethyl; R ^' represents an alkyl group with or without substituents having 1 to 6 carbon atoms, or a benzyl group with 7 carbon atoms without substituents; Wherein, the alkyl group having 1 to 6 carbon atoms may be methyl, ethyl, isopropyl, or butyl. In the above reaction formula, L*·Ni·Y represents a chiral catalyst of nickel, that is, an ionic compound of a complex of nickel and a chiral ligand and an anion. Among them, L* represents a chiral ligand, which is any ligand selected from L1 to L17. Y represents any one of chloride ion, bromide ion, acetate, trifluoroacetate, triflate and perchlorate.

In the method of preparing chiral glycine derivatives by asymmetric nickel catalytic hydrogenation of the present invention, from the viewpoint of reaction yield and reaction efficiency, the hydrogen pressure of the hydrogen atmosphere is 1 to 80 bar, and more preferably 1 to 50 bar.

In the method for preparing chiral glycine derivatives by asymmetric nickel catalytic hydrogenation of the present invention, from the viewpoint of reaction yield and reaction efficiency, the chiral catalyst of nickel and the N-aryl-α-imine represented by the general formula (1) The molar ratio of ester/amide is 1:20-10000, preferably 1:50-2000.

The method for preparing chiral glycine derivatives by asymmetric nickel catalytic hydrogenation of the present invention, from the viewpoint of reaction yield and reaction efficiency, the reaction temperature is -78°C to 100°C, and the preferred reaction temperature is -40°C to 40°C. A more preferred reaction temperature is 0°C to 30°C, a further preferred reaction temperature is 0°C to 70°C; the reaction time is 1 to 72 hours, the preferred reaction time is 5 to 60 hours, and the more preferred reaction time is 5 to 48 hours. , the reaction time is further preferably 5 to 36 hours, and the reaction time is particularly preferably 10 to 24 hours.

The present invention uses N-aryl-α-imide ester/amide represented by general formula (1) as a substrate, and performs asymmetric catalytic hydrogenation through a nickel chiral catalyst to obtain chiral glycine represented by general formula (2). derivative. The method of the invention has mild reaction conditions, is simple to operate, can achieve good reaction yield and reaction efficiency, and has good application effects.

In the following examples, according to the difference of R and R' substituents, 1a, 1b, 1c, 1d, 1e, 1f, 1g, 1h, 1i, 1J, 1k, 1l, 1m, 1n, 1o, 1p, 1q, 1r, 1s, 1t, 1u, 1v, 1w, 1x, 1y, 1z, 1aa, 1ab, 1ac, 1ad, 1ae, 1af, 1ag, 1ah, 1ai, 1aj, 1ak represent various different general formulas ( 1) Formula Z N-aryl-α-imide ester/amide represented by 2a, 2b, 2c, 2d, 2e, 2f, 2g, 2h, 2i, 2J, 2k, 2l, 2m, 2n, 2o, 2p, 2q, 2r, 2s, 2t, 2u, 2v, 2w, 2x, 2y, 2z, 2aa, 2ab, 2ac, 2ad, 2ae, 2af, 2ag, 2ah, 2ai, 2aj, 2ak represent various A chiral glycine compound represented by general formula (2).

In addition, it goes without saying that by the reaction method of the present invention, 1a is asymmetrically hydrogenated to produce 2a, 1b is asymmetrically hydrogenated to produce 2b, 1c is asymmetrically hydrogenated to produce 2c, 1d is asymmetrically hydrogenated to produce 2d, and 1e is asymmetrically hydrogenated. Hydrogenation produces 2e, asymmetric hydrogenation of 1f produces 2f, asymmetric hydrogenation of 1g produces 2g, asymmetric hydrogenation of 1h produces 2h, asymmetric hydrogenation of 1i produces 2i, asymmetric hydrogenation of 1J produces 2J, asymmetric hydrogenation of 1k produces 2k, 2l is generated from the asymmetric hydrogenation of 1l, 2m is generated from the asymmetric hydrogenation of 1n, 2n is generated from the asymmetric hydrogenation of 1n, 2o is generated from the asymmetric hydrogenation of 1o, 2p is generated from the asymmetric hydrogenation of 1p, 2q is generated from the asymmetric hydrogenation of 1q, as The asymmetric hydrogenation of 1r produces 2r, the asymmetric hydrogenation of 1s produces 2s, the asymmetric hydrogenation of 1t produces 2t, the asymmetric hydrogenation of 1u produces 2u, the asymmetric hydrogenation of 1v produces 2v, the asymmetric hydrogenation of 1w produces 2w, and the asymmetric hydrogenation of 1x produces 2w. Symmetric hydrogenation produces 2x, asymmetric hydrogenation of 1y produces 2y, asymmetric hydrogenation of 1z produces 2z, asymmetric hydrogenation of 1aa produces 2aa, asymmetric hydrogenation of 1ab produces 2ab, asymmetric hydrogenation of 1ac produces 2ac, asymmetric hydrogenation of 1ad 2ad is generated by asymmetric hydrogenation of 1ae, 2ae is generated by asymmetric hydrogenation of 1af, 2ag is generated by asymmetric hydrogenation of 1ag, 2ah is generated by asymmetric hydrogenation of 1ah, 2ai is generated by asymmetric hydrogenation of 1ai, 2aj is generated by asymmetric hydrogenation of 1aj , resulting from the asymmetric hydrogenation of 1ak to 2ak.

Moreover, in the following examples, as mentioned above, L*·Ni·Y represents a chiral catalyst of nickel, for example, L1·Ni·Cl represents a chiral catalyst composed of nickel, chiral ligand L1 and chloride ions. .

And in the following examples, according to the different Ar substituents, use L1a, L2a, L3a, L4a, L5a, L6a to represent L1-L6 where Ar is C ₆ H ₅ ; use L1b, L2b, L3b, L4b, L5b, L6b represents L1-L6 where Ar is 4-CH ₃ OC ₆ H ₄ ; L1c, L2c, L3c, L4c, L5c, L6c represents L1-L6 where Ar is 4-CF ₃ C ₆ H ₄ ; L1d, L2d, L3d, L4d, L5d, and L6d represent L1-L6 in which Ar is 3,5-di-tBu-4-MeOC6H2.

Example 1

Preparation of 2a (Ar=PMP (PMP=-p-MeOC ₆ H ₄ , p-methoxyphenyl), R=Ph, X=O, R'=CH3)

In a 10mL Schlenck tube, add phosphine ligand L1a (0.003mmol), nickel acetate tetrahydrate (0.75mg, 0.003mmol) and N-PMP-α-arylimide ester 1a (0.3mmol), and pass the system through a vacuum line , replace with nitrogen 3 times, add 1 mL of trifluoroethanol solvent, put it into the autoclave, after 6 times of hydrogen replacement, make the initial hydrogen pressure 30bar, stir and react at 50°C for 24 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 87% and the enantiomeric excess was 95%. 2a: White solid, 1H NMR (400MHz, Chloroform-d) δ7.48 (d, J＝7.2Hz, 2H), 7.40-7.26 (m, 3H), 6.71 (d, J＝8.8Hz, 2H), 6.52 (d, J=8.8Hz, 2H), 5.01 (s, 1H), 4.67 (s, 1H), 3.70 (s, 3H), 3.69 (s, 3H); 13C NMR (101MHz, Chloroform-d) δ 172. 8,152.8,140.5,138.1,129.1,128.5,127.5,115.1,115.0,61.9,55.9,53.0.

Example 2

Preparation of 2a (Ar=PMP, R=Ph, X=O, R'=CH ₃ )

In a 10mL Schlenck tube, add phosphine ligand L1b (0.003mmol), nickel acetate tetrahydrate (0.75mg, 0.003mmol) and N-PMP-α-arylimide ester 1a (0.3mmol), and pass the system through a vacuum line , replace with nitrogen 3 times, add 1 mL of trifluoroethanol solvent, put it into the autoclave, after 6 times of hydrogen replacement, make the initial hydrogen pressure 30bar, stir and react at 50°C for 24 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 92% and the enantiomeric excess was 94%. 2a: White solid, ¹ H NMR (400MHz, Chloroform-d) δ7.48 (d, J＝7.2Hz, 2H), 7.40-7.26 (m, 3H), 6.71 (d, J＝8.8Hz, 2H), 6.52(d,J＝8.8Hz,2H),5.01(s,1H),4.67(s,1H),3.70(s,3H),3.69(s,3H); ¹³ C NMR(101MHz,Chloroform-d) δ172.8,152.8,140.5,138.1,129.1,128.5,127.5,115.1,115.0,61.9,55.9,53.0.

Example 3

Preparation of 2a (Ar=PMP, R=Ph, X=O, R'=CH ₃ )

In a 10mL Schlenck tube, add the phosphine ligand L1c (0.003mmol), nickel acetate tetrahydrate (0.75mg, 0.003mmol) and N-PMP-α-arylimide ester 1a (0.3mmol), and pass the system through the vacuum line , replace with nitrogen 3 times, add 1 mL of trifluoroethanol solvent, put it into the autoclave, after 6 times of hydrogen replacement, make the initial hydrogen pressure 30bar, stir and react at 50°C for 24 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 95% and the enantiomeric excess was 95%. 2a: White solid, ¹ H NMR (400MHz, Chloroform-d) δ7.48 (d, J＝7.2Hz, 2H), 7.40-7.26 (m, 3H), 6.71 (d, J＝8.8Hz, 2H), 6.52(d,J＝8.8Hz,2H),5.01(s,1H),4.67(s,1H),3.70(s,3H),3.69(s,3H); ¹³ C NMR(101MHz,Chloroform-d) δ172.8,152.8,140.5,138.1,129.1,128.5,127.5,115.1,115.0,61.9,55.9,53.0.

Example 4

Preparation of 2a (Ar=PMP, R=Ph, X=O, R'=CH ₃ )

In a 10mL Schlenck tube, add phosphine ligand L1d (0.003mmol), nickel acetate tetrahydrate (0.75mg, 0.003mmol) and N-PMP-α-arylimide ester 1a (0.3mmol), and pass the system through a vacuum line , replace with nitrogen 3 times, add 1 mL of trifluoroethanol solvent, put it into the autoclave, after 6 times of hydrogen replacement, make the initial hydrogen pressure 30bar, stir and react at 50°C for 24 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 86% and the enantiomeric excess was 93%. 2a: White solid, ¹ H NMR (400MHz, Chloroform-d) δ7.48 (d, J＝7.2Hz, 2H), 7.40-7.26 (m, 3H), 6.71 (d, J＝8.8Hz, 2H), 6.52(d,J＝8.8Hz,2H),5.01(s,1H),4.67(s,1H),3.70(s,3H),3.69(s,3H); ¹³ C NMR(101MHz,Chloroform-d) δ172.8,152.8,140.5,138.1,129.1,128.5,127.5,115.1,115.0,61.9,55.9,53.0.

Example 5

Preparation of 2a (Ar=PMP, R=Ph, X=O, R'=CH ₃ )

In a 10mL Schlenck tube, add the phosphine ligand L2a (0.003mmol), nickel acetate tetrahydrate (0.75mg, 0.003mmol) and N-PMP-α-arylimide ester 1a (0.3mmol), and pass the system through the vacuum line , replace with nitrogen 3 times, add 1 mL of trifluoroethanol solvent, put it into the autoclave, after 6 times of hydrogen replacement, make the initial hydrogen pressure 30bar, stir and react at 50°C for 24 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 78% and the enantiomeric excess was 85%. 2a: White solid, ¹ H NMR (400MHz, Chloroform-d) δ7.48 (d, J＝7.2Hz, 2H), 7.40-7.26 (m, 3H), 6.71 (d, J＝8.8Hz, 2H), 6.52(d,J＝8.8Hz,2H),5.01(s,1H),4.67(s,1H),3.70(s,3H),3.69(s,3H); ¹³ C NMR(101MHz,Chloroform-d) δ172.8,152.8,140.5,138.1,129.1,128.5,127.5,115.1,115.0,61.9,55.9,53.0.

Example 6

Preparation of 2a (Ar=PMP, R=Ph, X=O, R'=CH ₃ )

In a 10mL Schlenck tube, add phosphine ligand L2b (0.003mmol), nickel acetate tetrahydrate (0.75mg, 0.003mmol) and N-PMP-α-arylimide ester 1a (0.3mmol), and pass the system through a vacuum line , replace with nitrogen 3 times, add 1 mL of trifluoroethanol solvent, put it into the autoclave, after 6 times of hydrogen replacement, make the initial hydrogen pressure 30bar, stir and react at 50°C for 24 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 82% and the enantiomeric excess was 90%. 2a: White solid, ¹ H NMR (400MHz, Chloroform-d) δ7.48 (d, J＝7.2Hz, 2H), 7.40-7.26 (m, 3H), 6.71 (d, J＝8.8Hz, 2H), 6.52(d,J＝8.8Hz,2H),5.01(s,1H),4.67(s,1H),3.70(s,3H),3.69(s,3H); ¹³ C NMR(101MHz,Chloroform-d) δ172.8,152.8,140.5,138.1,129.1,128.5,127.5,115.1,115.0,61.9,55.9,53.0.

Example 7

Preparation of 2a (Ar=PMP, R=Ph, X=O, R'=CH ₃ )

In a 10mL Schlenck tube, add the phosphine ligand L2c (0.003mmol), nickel acetate tetrahydrate (0.75mg, 0.003mmol) and N-PMP-α-arylimide ester 1a (0.3mmol), and pass the system through the vacuum line , replace with nitrogen 3 times, add 1 mL of trifluoroethanol solvent, put it into the autoclave, after 6 times of hydrogen replacement, make the initial hydrogen pressure 30bar, stir and react at 50°C for 24 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 65% and the enantiomeric excess was 67%. 2a: White solid, ¹ H NMR (400MHz, Chloroform-d) δ7.48 (d, J＝7.2Hz, 2H), 7.40-7.26 (m, 3H), 6.71 (d, J＝8.8Hz, 2H), 6.52(d,J＝8.8Hz,2H),5.01(s,1H),4.67(s,1H),3.70(s,3H),3.69(s,3H); ¹³ C NMR(101MHz,Chloroform-d) δ172.8,152.8,140.5,138.1,129.1,128.5,127.5,115.1,115.0,61.9,55.9,53.0.

Example 8

Preparation of 2a (Ar=PMP, R=Ph, X=O, R'=CH ₃ )

In a 10mL Schlenck tube, add the phosphine ligand L2d (0.003mmol), nickel acetate tetrahydrate (0.75mg, 0.003mmol) and N-PMP-α-arylimide ester 1a (0.3mmol), and pass the system through the vacuum line , replace with nitrogen 3 times, add 1 mL of trifluoroethanol solvent, put it into the autoclave, after 6 times of hydrogen replacement, make the initial hydrogen pressure 30bar, stir and react at 50°C for 24 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 67% and the enantiomeric excess was 88%. 2a: White solid, ¹ H NMR (400MHz, Chloroform-d) δ7.48 (d, J＝7.2Hz, 2H), 7.40-7.26 (m, 3H), 6.71 (d, J＝8.8Hz, 2H), 6.52(d,J＝8.8Hz,2H),5.01(s,1H),4.67(s,1H),3.70(s,3H),3.69(s,3H); ¹³ C NMR(101MHz,Chloroform-d) δ172.8,152.8,140.5,138.1,129.1,128.5,127.5,115.1,115.0,61.9,55.9,53.0.

Example 9

Preparation of 2a (Ar=PMP, R=Ph, X=O, R'=CH ₃ )

In a 10mL Schlenck tube, add phosphine ligand L3a (0.003mmol), nickel acetate tetrahydrate (0.75mg, 0.003mmol) and N-PMP-α-arylimide ester 1a (0.3mmol), and pass the system through a vacuum line , replace with nitrogen 3 times, add 1 mL of trifluoroethanol solvent, put it into the autoclave, after 6 times of hydrogen replacement, make the initial hydrogen pressure 30bar, stir and react at 50°C for 24 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 67% and the enantiomeric excess was 76%. 2a: White solid, ¹ H NMR (400MHz, Chloroform-d) δ7.48 (d, J＝7.2Hz, 2H), 7.40-7.26 (m, 3H), 6.71 (d, J＝8.8Hz, 2H), 6.52(d,J＝8.8Hz,2H),5.01(s,1H),4.67(s,1H),3.70(s,3H),3.69(s,3H); ¹³ C NMR(101MHz,Chloroform-d) δ172.8,152.8,140.5,138.1,129.1,128.5,127.5,115.1,115.0,61.9,55.9,53.0.

Example 10

Preparation of 2a (Ar=PMP, R=Ph, X=O, R'=CH ₃ )

In a 10mL Schlenck tube, add phosphine ligand L3b (0.003mmol), nickel acetate tetrahydrate (0.75mg, 0.003mmol) and N-PMP-α-arylimide ester 1a (0.3mmol), and pass the system through a vacuum line , replace with nitrogen 3 times, add 1 mL of trifluoroethanol solvent, put it into the autoclave, after 6 times of hydrogen replacement, make the initial hydrogen pressure 30bar, stir and react at 50°C for 24 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 80% and the enantiomeric excess was 84%. 2a: White solid, ¹ H NMR (400MHz, Chloroform-d) δ7.48 (d, J＝7.2Hz, 2H), 7.40-7.26 (m, 3H), 6.71 (d, J＝8.8Hz, 2H), 6.52(d,J＝8.8Hz,2H),5.01(s,1H),4.67(s,1H),3.70(s,3H),3.69(s,3H); ¹³ C NMR(101MHz,Chloroform-d) δ172.8,152.8,140.5,138.1,129.1,128.5,127.5,115.1,115.0,61.9,55.9,53.0.

Example 11

Preparation of 2a (Ar=PMP, R=Ph, X=O, R'=CH ₃ )

In a 10mL Schlenck tube, add the phosphine ligand L3c (0.003mmol), nickel acetate tetrahydrate (0.75mg, 0.003mmol) and N-PMP-α-arylimide ester 1a (0.3mmol), and pass the system through the vacuum line , replace with nitrogen 3 times, add 1 mL of trifluoroethanol solvent, put it into the autoclave, after 6 times of hydrogen replacement, make the initial hydrogen pressure 30bar, stir and react at 50°C for 24 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 72% and the enantiomeric excess was 87%. 2a: White solid, ¹ H NMR (400MHz, Chloroform-d) δ7.48 (d, J＝7.2Hz, 2H), 7.40-7.26 (m, 3H), 6.71 (d, J＝8.8Hz, 2H), 6.52(d,J＝8.8Hz,2H),5.01(s,1H),4.67(s,1H),3.70(s,3H),3.69(s,3H); ¹³ C NMR(101MHz,Chloroform-d) δ172.8,152.8,140.5,138.1,129.1,128.5,127.5,115.1,115.0,61.9,55.9,53.0.

Example 12

Preparation of 2a (Ar=PMP, R=Ph, X=O, R'=CH ₃ )

In a 10mL Schlenck tube, add the phosphine ligand L3d (0.003mmol), nickel acetate tetrahydrate (0.75mg, 0.003mmol) and N-PMP-α-arylimide ester 1a (0.3mmol), and pass the system through the vacuum line , replace with nitrogen 3 times, add 1 mL of trifluoroethanol solvent, put it into the autoclave, after 6 times of hydrogen replacement, make the initial hydrogen pressure 30bar, stir and react at 50°C for 24 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 91% and the enantiomeric excess was 92%. 2a: White solid, ¹ H NMR (400MHz, Chloroform-d) δ7.48 (d, J＝7.2Hz, 2H), 7.40-7.26 (m, 3H), 6.71 (d, J＝8.8Hz, 2H), 6.52(d,J＝8.8Hz,2H),5.01(s,1H),4.67(s,1H),3.70(s,3H),3.69(s,3H); ¹³ C NMR(101MHz,Chloroform-d) δ172.8,152.8,140.5,138.1,129.1,128.5,127.5,115.1,115.0,61.9,55.9,53.0.

Example 13

Preparation of 2a (Ar=PMP, R=Ph, X=O, R'=CH ₃ )

In a 10mL Schlenck tube, add phosphine ligand L4a (0.003mmol), nickel acetate tetrahydrate (0.75mg, 0.003mmol) and N-PMP-α-arylimide ester 1a (0.3mmol), and the system is passed through the vacuum line , replace with nitrogen 3 times, add 1 mL of trifluoroethanol solvent, put it into the autoclave, after 6 times of hydrogen replacement, make the initial hydrogen pressure 30bar, stir and react at 50°C for 24 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 77% and the enantiomeric excess was 82%. 2a: White solid, ¹ H NMR (400MHz, Chloroform-d) δ7.48 (d, J＝7.2Hz, 2H), 7.40-7.26 (m, 3H), 6.71 (d, J＝8.8Hz, 2H), 6.52(d,J＝8.8Hz,2H),5.01(s,1H),4.67(s,1H),3.70(s,3H),3.69(s,3H); ¹³ C NMR(101MHz,Chloroform-d) δ172.8,152.8,140.5,138.1,129.1,128.5,127.5,115.1,115.0,61.9,55.9,53.0.

Example 14

Preparation of 2a (Ar=PMP, R=Ph, X=O, R'=CH ₃ )

In a 10mL Schlenck tube, add phosphine ligand L4b (0.003mmol), nickel acetate tetrahydrate (0.75mg, 0.003mmol) and N-PMP-α-arylimide ester 1a (0.3mmol), and pass the system through a vacuum line , replace with nitrogen 3 times, add 1 mL of trifluoroethanol solvent, put it into the autoclave, after 6 times of hydrogen replacement, make the initial hydrogen pressure 30bar, stir and react at 50°C for 24 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 74% and the enantiomeric excess was 86%. 2a: White solid, ¹ H NMR (400MHz, Chloroform-d) δ7.48 (d, J＝7.2Hz, 2H), 7.40-7.26 (m, 3H), 6.71 (d, J＝8.8Hz, 2H), 6.52(d,J＝8.8Hz,2H),5.01(s,1H),4.67(s,1H),3.70(s,3H),3.69(s,3H); ¹³ C NMR(101MHz,Chloroform-d) δ172.8,152.8,140.5,138.1,129.1,128.5,127.5,115.1,115.0,61.9,55.9,53.0.

Example 15

Preparation of 2a (Ar=PMP, R=Ph, X=O, R'=CH ₃ )

In a 10mL Schlenck tube, add the phosphine ligand L4c (0.003mmol), nickel acetate tetrahydrate (0.75mg, 0.003mmol) and N-PMP-α-arylimide ester 1a (0.3mmol), and pass the system through the vacuum line , replace with nitrogen 3 times, add 1 mL of trifluoroethanol solvent, put it into the autoclave, after 6 times of hydrogen replacement, make the initial hydrogen pressure 30bar, stir and react at 50°C for 24 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 87% and the enantiomeric excess was 92%. 2a: White solid, ¹ H NMR (400MHz, Chloroform-d) δ7.48 (d, J＝7.2Hz, 2H), 7.40-7.26 (m, 3H), 6.71 (d, J＝8.8Hz, 2H), 6.52(d,J＝8.8Hz,2H),5.01(s,1H),4.67(s,1H),3.70(s,3H),3.69(s,3H); ¹³ C NMR(101MHz,Chloroform-d) δ172.8,152.8,140.5,138.1,129.1,128.5,127.5,115.1,115.0,61.9,55.9,53.0.

Example 16

Preparation of 2a (Ar=PMP, R=Ph, X=O, R'=CH ₃ )

In a 10mL Schlenck tube, add the phosphine ligand L4d (0.003mmol), nickel acetate tetrahydrate (0.75mg, 0.003mmol) and N-PMP-α-arylimide ester 1a (0.3mmol), and pass the system through the vacuum line , replace with nitrogen 3 times, add 1 mL of trifluoroethanol solvent, put it into the autoclave, after 6 times of hydrogen replacement, make the initial hydrogen pressure 30bar, stir and react at 50°C for 24 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 99% and the enantiomeric excess was 83%. 2a: White solid, ¹ H NMR (400MHz, Chloroform-d) δ7.48 (d, J＝7.2Hz, 2H), 7.40-7.26 (m, 3H), 6.71 (d, J＝8.8Hz, 2H), 6.52(d,J＝8.8Hz,2H),5.01(s,1H),4.67(s,1H),3.70(s,3H),3.69(s,3H); ¹³ C NMR(101MHz,Chloroform-d) δ172.8,152.8,140.5,138.1,129.1,128.5,127.5,115.1,115.0,61.9,55.9,53.0.

Example 17

Preparation of 2a (Ar=PMP, R=Ph, X=O, R'=CH ₃ )

In a 10mL Schlenck tube, add phosphine ligand L5a (0.003mmol), nickel acetate tetrahydrate (0.75mg, 0.003mmol) and N-PMP-α-arylimide ester 1a (0.3mmol), and pass the system through a vacuum line , replace with nitrogen 3 times, add 1 mL of trifluoroethanol solvent, put it into the autoclave, after 6 times of hydrogen replacement, make the initial hydrogen pressure 30bar, stir and react at 50°C for 24 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 50% and the enantiomeric excess was 84%. 2a: White solid, ¹ H NMR (400MHz, Chloroform-d) δ7.48 (d, J＝7.2Hz, 2H), 7.40-7.26 (m, 3H), 6.71 (d, J＝8.8Hz, 2H), 6.52(d,J＝8.8Hz,2H),5.01(s,1H),4.67(s,1H),3.70(s,3H),3.69(s,3H); ¹³ C NMR(101MHz,Chloroform-d) δ172.8,152.8,140.5,138.1,129.1,128.5,127.5,115.1,115.0,61.9,55.9,53.0.

Example 18

Preparation of 2a (Ar=PMP, R=Ph, X=O, R'=CH ₃ )

In a 10mL Schlenck tube, add phosphine ligand L5b (0.003mmol), nickel acetate tetrahydrate (0.75mg, 0.003mmol) and N-PMP-α-arylimide ester 1a (0.3mmol), and pass the system through a vacuum line , replace with nitrogen 3 times, add 1 mL of trifluoroethanol solvent, put it into the autoclave, after 6 times of hydrogen replacement, make the initial hydrogen pressure 30bar, stir and react at 50°C for 24 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 81% and the enantiomeric excess was 75%. 2a: White solid, ¹ H NMR (400MHz, Chloroform-d) δ7.48 (d, J＝7.2Hz, 2H), 7.40-7.26 (m, 3H), 6.71 (d, J＝8.8Hz, 2H), 6.52(d,J＝8.8Hz,2H),5.01(s,1H),4.67(s,1H),3.70(s,3H),3.69(s,3H); ¹³ C NMR(101MHz,Chloroform-d) δ172.8,152.8,140.5,138.1,129.1,128.5,127.5,115.1,115.0,61.9,55.9,53.0.

Example 19

Preparation of 2a (Ar=PMP, R=Ph, X=O, R'=CH ₃ )

In a 10mL Schlenck tube, add phosphine ligand L5c (0.003mmol), nickel acetate tetrahydrate (0.75mg, 0.003mmol) and N-PMP-α-arylimide ester 1a (0.3mmol), and pass the system through a vacuum line , replace with nitrogen 3 times, add 1 mL of trifluoroethanol solvent, put it into the autoclave, after 6 times of hydrogen replacement, make the initial hydrogen pressure 30bar, stir and react at 50°C for 24 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 86% and the enantiomeric excess was 85%. 2a: White solid, ¹ H NMR (400MHz, Chloroform-d) δ7.48 (d, J＝7.2Hz, 2H), 7.40-7.26 (m, 3H), 6.71 (d, J＝8.8Hz, 2H), 6.52(d,J＝8.8Hz,2H),5.01(s,1H),4.67(s,1H),3.70(s,3H),3.69(s,3H); ¹³ C NMR(101MHz,Chloroform-d) δ172.8,152.8,140.5,138.1,129.1,128.5,127.5,115.1,115.0,61.9,55.9,53.0.

Example 20

Preparation of 2a (Ar=PMP, R=Ph, X=O, R'=CH ₃ )

In a 10mL Schlenck tube, add the phosphine ligand L5d (0.003mmol), nickel acetate tetrahydrate (0.75mg, 0.003mmol) and N-PMP-α-arylimide ester 1a (0.3mmol), and pass the system through the vacuum line , replace with nitrogen 3 times, add 1 mL of trifluoroethanol solvent, put it into the autoclave, after 6 times of hydrogen replacement, make the initial hydrogen pressure 30bar, stir and react at 50°C for 24 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 95% and the enantiomeric excess was 93%. 2a: White solid, ¹ H NMR (400MHz, Chloroform-d) δ7.48 (d, J＝7.2Hz, 2H), 7.40-7.26 (m, 3H), 6.71 (d, J＝8.8Hz, 2H), 6.52(d,J＝8.8Hz,2H),5.01(s,1H),4.67(s,1H),3.70(s,3H),3.69(s,3H); ¹³ C NMR(101MHz,Chloroform-d) δ172.8,152.8,140.5,138.1,129.1,128.5,127.5,115.1,115.0,61.9,55.9,53.0.

Example 21

Preparation of 2a (Ar=PMP, R=Ph, X=O, R'=CH ₃ )

In a 10mL Schlenck tube, add phosphine ligand L6a (0.003mmol), nickel acetate tetrahydrate (0.75mg, 0.003mmol) and N-PMP-α-arylimide ester 1a (0.3mmol), and pass the system through a vacuum line , replace with nitrogen 3 times, add 1 mL of trifluoroethanol solvent, put it into the autoclave, after 6 times of hydrogen replacement, make the initial hydrogen pressure 30bar, stir and react at 50°C for 24 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 75% and the enantiomeric excess was 76%. 2a: White solid, ¹ H NMR (400MHz, Chloroform-d) δ7.48 (d, J＝7.2Hz, 2H), 7.40-7.26 (m, 3H), 6.71 (d, J＝8.8Hz, 2H), 6.52(d,J＝8.8Hz,2H),5.01(s,1H),4.67(s,1H),3.70(s,3H),3.69(s,3H); ¹³ C NMR(101MHz,Chloroform-d) δ172.8,152.8,140.5,138.1,129.1,128.5,127.5,115.1,115.0,61.9,55.9,53.0.

Example 22

Preparation of 2a (Ar=PMP, R=Ph, X=O, R'=CH ₃ )

In a 10mL Schlenck tube, add phosphine ligand L6b (0.003mmol), nickel acetate tetrahydrate (0.75mg, 0.003mmol) and N-PMP-α-arylimide ester 1a (0.3mmol), and pass the system through a vacuum line , replace with nitrogen 3 times, add 1 mL of trifluoroethanol solvent, put it into the autoclave, after 6 times of hydrogen replacement, make the initial hydrogen pressure 30bar, stir and react at 50°C for 24 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 78% and the enantiomeric excess was 84%. 2a: White solid, ¹ H NMR (400MHz, Chloroform-d) δ7.48 (d, J＝7.2Hz, 2H), 7.40-7.26 (m, 3H), 6.71 (d, J＝8.8Hz, 2H), 6.52(d,J＝8.8Hz,2H),5.01(s,1H),4.67(s,1H),3.70(s,3H),3.69(s,3H); ¹³ C NMR(101MHz,Chloroform-d) δ172.8,152.8,140.5,138.1,129.1,128.5,127.5,115.1,115.0,61.9,55.9,53.0.

Example 23

Preparation of 2a (Ar=PMP, R=Ph, X=O, R'=CH ₃ )

In a 10mL Schlenck tube, add the phosphine ligand L6c (0.003mmol), nickel acetate tetrahydrate (0.75mg, 0.003mmol) and N-PMP-α-arylimide ester 1a (0.3mmol), and pass the system through the vacuum line , replace with nitrogen 3 times, add 1 mL of trifluoroethanol solvent, put it into the autoclave, after 6 times of hydrogen replacement, make the initial hydrogen pressure 30bar, stir and react at 50°C for 24 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 88% and the enantiomeric excess was 85%. 2a: White solid, ¹ H NMR (400MHz, Chloroform-d) δ7.48 (d, J＝7.2Hz, 2H), 7.40-7.26 (m, 3H), 6.71 (d, J＝8.8Hz, 2H), 6.52(d,J＝8.8Hz,2H),5.01(s,1H),4.67(s,1H),3.70(s,3H),3.69(s,3H); ¹³ C NMR(101MHz,Chloroform-d) δ172.8,152.8,140.5,138.1,129.1,128.5,127.5,115.1,115.0,61.9,55.9,53.0.

Example 24

Preparation of 2a (Ar=PMP, R=Ph, X=O, R'=CH ₃ )

In a 10mL Schlenck tube, add phosphine ligand L6d (0.003mmol), nickel acetate tetrahydrate (0.75mg, 0.003mmol) and N-PMP-α-arylimide ester 1a (0.3mmol), and pass the system through a vacuum line , replace with nitrogen 3 times, add 1 mL of trifluoroethanol solvent, put it into the autoclave, after 6 times of hydrogen replacement, make the initial hydrogen pressure 30bar, stir and react at 50°C for 24 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 94% and the enantiomeric excess was 96%. 2a: White solid, ¹ H NMR (400MHz, Chloroform-d) δ7.48 (d, J＝7.2Hz, 2H), 7.40-7.26 (m, 3H), 6.71 (d, J＝8.8Hz, 2H), 6.52(d,J＝8.8Hz,2H),5.01(s,1H),4.67(s,1H),3.70(s,3H),3.69(s,3H); ¹³ C NMR(101MHz,Chloroform-d) δ172.8,152.8,140.5,138.1,129.1,128.5,127.5,115.1,115.0,61.9,55.9,53.0.

Example 25

Preparation of 2a (Ar=PMP, R=Ph, X=O, R'=CH ₃ )

In a 10mL Schlenck tube, add phosphine ligand L7 (0.003mmol), nickel acetate tetrahydrate (0.75mg, 0.003mmol) and N-PMP-α-arylimide ester 1a (0.3mmol), and pass the system through a vacuum line , replace with nitrogen 3 times, add 1 mL of trifluoroethanol solvent, put it into the autoclave, after 6 times of hydrogen replacement, make the initial hydrogen pressure 30bar, stir and react at 50°C for 24 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 99% and the enantiomeric excess was 96%. 2a: White solid, ¹ H NMR (400MHz, Chloroform-d) δ7.48 (d, J＝7.2Hz, 2H), 7.40-7.26 (m, 3H), 6.71 (d, J＝8.8Hz, 2H), 6.52(d,J＝8.8Hz,2H),5.01(s,1H),4.67(s,1H),3.70(s,3H),3.69(s,3H); ¹³ C NMR(101MHz,Chloroform-d) δ172.8,152.8,140.5,138.1,129.1,128.5,127.5,115.1,115.0,61.9,55.9,53.0.

Example 26

Preparation of 2a (Ar=PMP, R=Ph, X=O, R'=CH ₃ )

In a 10mL Schlenck tube, add phosphine ligand L8 (0.003mmol), nickel acetate tetrahydrate (0.75mg, 0.003mmol) and N-PMP-α-arylimide ester 1a (0.3mmol), and pass the system through a vacuum line , replace with nitrogen 3 times, add 1 mL of trifluoroethanol solvent, put it into the autoclave, after 6 times of hydrogen replacement, make the initial hydrogen pressure 30bar, stir and react at 50°C for 24 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 99% and the enantiomeric excess was 92%. 2a: White solid, ¹ H NMR (400MHz, Chloroform-d) δ7.48 (d, J＝7.2Hz, 2H), 7.40-7.26 (m, 3H), 6.71 (d, J＝8.8Hz, 2H), 6.52(d,J＝8.8Hz,2H),5.01(s,1H),4.67(s,1H),3.70(s,3H),3.69(s,3H); ¹³ C NMR(101MHz,Chloroform-d) δ172.8,152.8,140.5,138.1,129.1,128.5,127.5,115.1,115.0,61.9,55.9,53.0.

Example 27

Preparation of 2a (Ar=PMP, R=Ph, X=O, R'=CH ₃ )

In a 10mL Schlenck tube, add phosphine ligand L9 (0.003mmol), nickel acetate tetrahydrate (0.75mg, 0.003mmol) and N-PMP-α-arylimide ester 1a (0.3mmol), and pass the system through a vacuum line , replace with nitrogen 3 times, add 1 mL of trifluoroethanol solvent, put it into the autoclave, after 6 times of hydrogen replacement, make the initial hydrogen pressure 30bar, stir and react at 50°C for 24 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 87% and the enantiomeric excess was 95%. 2a: White solid, ¹ H NMR (400MHz, Chloroform-d) δ7.48 (d, J＝7.2Hz, 2H), 7.40-7.26 (m, 3H), 6.71 (d, J＝8.8Hz, 2H), 6.52(d,J＝8.8Hz,2H),5.01(s,1H),4.67(s,1H),3.70(s,3H),3.69(s,3H); ¹³ C NMR(101MHz,Chloroform-d) δ172.8,152.8,140.5,138.1,129.1,128.5,127.5,115.1,115.0,61.9,55.9,53.0.

Example 28

Preparation of 2a (Ar=PMP, R=Ph, X=O, R'=CH ₃ )

In a 10mL Schlenck tube, add phosphine ligand L10 (0.003mmol), nickel acetate tetrahydrate (0.75mg, 0.003mmol) and N-PMP-α-arylimide ester 1a (0.3mmol), and pass the system through a vacuum line , replace with nitrogen 3 times, add 1 mL of trifluoroethanol solvent, put it into the autoclave, after 6 times of hydrogen replacement, make the initial hydrogen pressure 30bar, stir and react at 50°C for 24 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 85% and the enantiomeric excess was 86%. 2a: White solid, ¹ H NMR (400MHz, Chloroform-d) δ7.48 (d, J＝7.2Hz, 2H), 7.40-7.26 (m, 3H), 6.71 (d, J＝8.8Hz, 2H), 6.52(d,J＝8.8Hz,2H),5.01(s,1H),4.67(s,1H),3.70(s,3H),3.69(s,3H); ¹³ C NMR(101MHz,Chloroform-d) δ172.8,152.8,140.5,138.1,129.1,128.5,127.5,115.1,115.0,61.9,55.9,53.0.

Example 29

Preparation of 2a (Ar=PMP, R=Ph, X=O, R'=CH ₃ )

In a 10mL Schlenck tube, add phosphine ligand L11 (0.003mmol), nickel acetate tetrahydrate (0.75mg, 0.003mmol) and N-PMP-α-arylimide ester 1a (0.3mmol), and pass the system through a vacuum line , replace with nitrogen 3 times, add 1 mL of trifluoroethanol solvent, put it into the autoclave, after 6 times of hydrogen replacement, make the initial hydrogen pressure 30bar, stir and react at 50°C for 24 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 95% and the enantiomeric excess was 90%. 2a: White solid, ¹ H NMR (400MHz, Chloroform-d) δ7.48 (d, J＝7.2Hz, 2H), 7.40-7.26 (m, 3H), 6.71 (d, J＝8.8Hz, 2H), 6.52(d,J＝8.8Hz,2H),5.01(s,1H),4.67(s,1H),3.70(s,3H),3.69(s,3H); ¹³ C NMR(101MHz,Chloroform-d) δ172.8,152.8,140.5,138.1,129.1,128.5,127.5,115.1,115.0,61.9,55.9,53.0.

Example 30

Preparation of 2a (Ar=PMP, R=Ph, X=O, R'=CH ₃ )

In a 10mL Schlenck tube, add phosphine ligand L12 (0.003mmol), nickel acetate tetrahydrate (0.75mg, 0.003mmol) and N-PMP-α-arylimide ester 1a (0.3mmol), and pass the system through a vacuum line , replace with nitrogen 3 times, add 1 mL of trifluoroethanol solvent, put it into the autoclave, after 6 times of hydrogen replacement, make the initial hydrogen pressure 30bar, stir and react at 50°C for 24 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 81% and the enantiomeric excess was 86%. 2a: White solid, ¹ H NMR (400MHz, Chloroform-d) δ7.48 (d, J＝7.2Hz, 2H), 7.40-7.26 (m, 3H), 6.71 (d, J＝8.8Hz, 2H), 6.52(d,J＝8.8Hz,2H),5.01(s,1H),4.67(s,1H),3.70(s,3H),3.69(s,3H); ¹³ C NMR(101MHz,Chloroform-d) δ172.8,152.8,140.5,138.1,129.1,128.5,127.5,115.1,115.0,61.9,55.9,53.0.

Example 31

Preparation of 2a (Ar=PMP, R=Ph, X=O, R'=CH ₃ )

In a 10mL Schlenck tube, add phosphine ligand L13 (0.003mmol), nickel acetate tetrahydrate (0.75mg, 0.003mmol) and N-PMP-α-arylimide ester 1a (0.3mmol), and pass the system through a vacuum line , replace with nitrogen 3 times, add 1 mL of trifluoroethanol solvent, put it into the autoclave, after 6 times of hydrogen replacement, make the initial hydrogen pressure 30bar, stir and react at 50°C for 24 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 95% and the enantiomeric excess was 65%. 2a: White solid, ¹ H NMR (400MHz, Chloroform-d) δ7.48 (d, J＝7.2Hz, 2H), 7.40-7.26 (m, 3H), 6.71 (d, J＝8.8Hz, 2H), 6.52(d,J＝8.8Hz,2H),5.01(s,1H),4.67(s,1H),3.70(s,3H),3.69(s,3H); ¹³ C NMR(101MHz,Chloroform-d) δ172.8,152.8,140.5,138.1,129.1,128.5,127.5,115.1,115.0,61.9,55.9,53.0.

Example 32

Preparation of 2a (Ar=PMP, R=Ph, X=O, R'=CH ₃ )

In a 10mL Schlenck tube, add phosphine ligand L14 (0.003mmol), nickel acetate tetrahydrate (0.75mg, 0.003mmol) and N-PMP-α-arylimide ester 1a (0.3mmol), and pass the system through a vacuum line , replace with nitrogen 3 times, add 1 mL of trifluoroethanol solvent, put it into the autoclave, after 6 times of hydrogen replacement, make the initial hydrogen pressure 30bar, stir and react at 50°C for 24 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 80% and the enantiomeric excess was 75%. 2a: White solid, ¹ H NMR (400MHz, Chloroform-d) δ7.48 (d, J＝7.2Hz, 2H), 7.40-7.26 (m, 3H), 6.71 (d, J＝8.8Hz, 2H), 6.52(d,J＝8.8Hz,2H),5.01(s,1H),4.67(s,1H),3.70(s,3H),3.69(s,3H); ¹³ C NMR(101MHz,Chloroform-d) δ172.8,152.8,140.5,138.1,129.1,128.5,127.5,115.1,115.0,61.9,55.9,53.0.

Example 33

Preparation of 2a (Ar=PMP, R=Ph, X=O, R'=CH ₃ )

In a 10mL Schlenck tube, add phosphine ligand L15 (0.003mmol), nickel acetate tetrahydrate (0.75mg, 0.003mmol) and N-PMP-α-arylimide ester 1a (0.3mmol), and pass the system through a vacuum line , replace with nitrogen 3 times, add 1 mL of trifluoroethanol solvent, put it into the autoclave, after 6 times of hydrogen replacement, make the initial hydrogen pressure 30bar, stir and react at 50°C for 24 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 87% and the enantiomeric excess was 79%. 2a: White solid, ¹ H NMR (400MHz, Chloroform-d) δ7.48 (d, J＝7.2Hz, 2H), 7.40-7.26 (m, 3H), 6.71 (d, J＝8.8Hz, 2H), 6.52(d,J＝8.8Hz,2H),5.01(s,1H),4.67(s,1H),3.70(s,3H),3.69(s,3H); ¹³ C NMR(101MHz,Chloroform-d) δ172.8,152.8,140.5,138.1,129.1,128.5,127.5,115.1,115.0,61.9,55.9,53.0.

Example 34

Preparation of 2a (Ar=PMP, R=Ph, X=O, R'=CH ₃ )

In a 10mL Schlenck tube, add phosphine ligand L16 (0.003mmol), nickel acetate tetrahydrate (0.75mg, 0.003mmol) and N-PMP-α-arylimide ester 1a (0.3mmol), and pass the system through a vacuum line , replace with nitrogen 3 times, add 1 mL of trifluoroethanol solvent, put it into the autoclave, after 6 times of hydrogen replacement, make the initial hydrogen pressure 30bar, stir and react at 50°C for 24 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 79% and the enantiomeric excess was 59%. 2a: White solid, ¹ H NMR (400MHz, Chloroform-d) δ7.48 (d, J＝7.2Hz, 2H), 7.40-7.26 (m, 3H), 6.71 (d, J＝8.8Hz, 2H), 6.52(d,J＝8.8Hz,2H),5.01(s,1H),4.67(s,1H),3.70(s,3H),3.69(s,3H); ¹³ C NMR(101MHz,Chloroform-d) δ172.8,152.8,140.5,138.1,129.1,128.5,127.5,115.1,115.0,61.9,55.9,53.0.

Example 35

Preparation of 2a (Ar=PMP, R=Ph, X=O, R'=CH ₃ )

In a 10mL Schlenck tube, add phosphine ligand L17 (0.003mmol), nickel acetate tetrahydrate (0.75mg, 0.003mmol) and N-PMP-α-arylimide ester 1a (0.3mmol), and pass the system through a vacuum line , replace with nitrogen 3 times, add 1 mL of trifluoroethanol solvent, put it into the autoclave, after 6 times of hydrogen replacement, make the initial hydrogen pressure 30bar, stir and react at 50°C for 24 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 61% and the enantiomeric excess was 69%. 2a: White solid, ¹ H NMR (400MHz, Chloroform-d) δ7.48 (d, J＝7.2Hz, 2H), 7.40-7.26 (m, 3H), 6.71 (d, J＝8.8Hz, 2H), 6.52(d,J＝8.8Hz,2H),5.01(s,1H),4.67(s,1H),3.70(s,3H),3.69(s,3H); ¹³ C NMR(101MHz,Chloroform-d) δ172.8,152.8,140.5,138.1,129.1,128.5,127.5,115.1,115.0,61.9,55.9,53.0.

Example 36

Preparation of 2a (Ar=PMP, R=Ph, X=O, R'=CH ₃ )

In a 10mL Schlenck tube, add phosphine ligand L7 (0.003mmol), nickel acetate tetrahydrate (0.75mg, 0.003mmol) and N-PMP-α-arylimide ester 1a (0.3mmol), and pass the system through a vacuum line , replace with nitrogen 3 times, add 1 mL of tetrahydrofuran solvent, put it into the autoclave, after 6 times of hydrogen replacement, make the initial hydrogen pressure 30bar, stir and react at 50°C for 24 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 63% and the enantiomeric excess was 78%. 2a: White solid, ¹ H NMR (400MHz, Chloroform-d) δ7.48 (d, J＝7.2Hz, 2H), 7.40-7.26 (m, 3H), 6.71 (d, J＝8.8Hz, 2H), 6.52(d,J＝8.8Hz,2H),5.01(s,1H),4.67(s,1H),3.70(s,3H),3.69(s,3H); ¹³ C NMR(101MHz,Chloroform-d) δ172.8,152.8,140.5,138.1,129.1,128.5,127.5,115.1,115.0,61.9,55.9,53.0.

Example 37

Preparation of 2a (Ar=PMP, R=Ph, X=O, R'=CH ₃ )

In a 10mL Schlenck tube, add phosphine ligand L7 (0.003mmol), nickel acetate tetrahydrate (0.75mg, 0.003mmol) and N-PMP-α-arylimide ester 1a (0.3mmol), and pass the system through a vacuum line , replace with nitrogen 3 times, add 1 mL of methanol solvent, put it into the autoclave, after 6 times of hydrogen replacement, make the initial hydrogen pressure 30bar, stir and react at 50°C for 24 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 99% and the enantiomeric excess was 43%. 2a: White solid, ¹ H NMR (400MHz, Chloroform-d) δ7.48 (d, J＝7.2Hz, 2H), 7.40-7.26 (m, 3H), 6.71 (d, J＝8.8Hz, 2H), 6.52(d,J＝8.8Hz,2H),5.01(s,1H),4.67(s,1H),3.70(s,3H),3.69(s,3H); ¹³ C NMR(101MHz,Chloroform-d) δ172.8,152.8,140.5,138.1,129.1,128.5,127.5,115.1,115.0,61.9,55.9,53.0.

Example 38

Preparation of 2a (Ar=PMP, R=Ph, X=O, R'=CH ₃ )

In a 10mL Schlenck tube, add phosphine ligand L7 (0.003mmol), nickel acetate tetrahydrate (0.75mg, 0.003mmol) and N-PMP-α-arylimide ester 1a (0.3mmol), and pass the system through a vacuum line , replace with nitrogen 3 times, add 1 mL of ethanol solvent, put it into the autoclave, after 6 times of hydrogen replacement, make the initial hydrogen pressure 30bar, stir and react at 50°C for 24 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 58% and the enantiomeric excess was 50%. 2a: White solid, ¹ H NMR (400MHz, Chloroform-d) δ7.48 (d, J＝7.2Hz, 2H), 7.40-7.26 (m, 3H), 6.71 (d, J＝8.8Hz, 2H), 6.52(d,J＝8.8Hz,2H),5.01(s,1H),4.67(s,1H),3.70(s,3H),3.69(s,3H); ¹³ C NMR(101MHz,Chloroform-d) δ172.8,152.8,140.5,138.1,129.1,128.5,127.5,115.1,115.0,61.9,55.9,53.0.

Example 39

Preparation of 2a (Ar=PMP, R=Ph, X=O, R'=CH ₃ )

In a 10mL Schlenck tube, add phosphine ligand L7 (0.003mmol), nickel acetate tetrahydrate (0.75mg, 0.003mmol) and N-PMP-α-arylimide ester 1a (0.3mmol), and pass the system through a vacuum line , replace with nitrogen 3 times, add 1 mL of isopropyl alcohol solvent, put it into the autoclave, after 6 times of hydrogen replacement, make the initial hydrogen pressure 30bar, stir and react at 50°C for 24 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 86% and the enantiomeric excess was 90%. 2a: White solid, ¹ H NMR (400MHz, Chloroform-d) δ7.48 (d, J＝7.2Hz, 2H), 7.40-7.26 (m, 3H), 6.71 (d, J＝8.8Hz, 2H), 6.52(d,J＝8.8Hz,2H),5.01(s,1H),4.67(s,1H),3.70(s,3H),3.69(s,3H); ¹³ C NMR(101MHz,Chloroform-d) δ172.8,152.8,140.5,138.1,129.1,128.5,127.5,115.1,115.0,61.9,55.9,53.0.

Example 40

Preparation of 2a (Ar=PMP, R=Ph, X=O, R'=CH ₃ )

In a 10mL Schlenck tube, add phosphine ligand L7 (0.003mmol), nickel acetate tetrahydrate (0.75mg, 0.003mmol) and N-PMP-α-arylimide ester 1a (0.3mmol), and pass the system through a vacuum line , replace with nitrogen 3 times, add 1 mL of acetone solvent, put it into the autoclave, after 6 times of hydrogen replacement, make the initial hydrogen pressure 30bar, stir and react at 50°C for 24 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 64% and the enantiomeric excess was 78%. 2a: White solid, ¹ H NMR (400MHz, Chloroform-d) δ7.48 (d, J＝7.2Hz, 2H), 7.40-7.26 (m, 3H), 6.71 (d, J＝8.8Hz, 2H), 6.52(d,J＝8.8Hz,2H),5.01(s,1H),4.67(s,1H),3.70(s,3H),3.69(s,3H); ¹³ C NMR(101MHz,Chloroform-d) δ172.8,152.8,140.5,138.1,129.1,128.5,127.5,115.1,115.0,61.9,55.9,53.0.

Example 41

Preparation of 2a (Ar=PMP, R=Ph, X=O, R'=CH ₃ )

In a 10mL Schlenck tube, add phosphine ligand L7 (0.003mmol), nickel acetate tetrahydrate (0.75mg, 0.003mmol) and N-PMP-α-arylimide ester 1a (0.3mmol), and pass the system through a vacuum line , replace with nitrogen 3 times, add 1 mL of acetonitrile solvent, put it into the autoclave, after 6 times of hydrogen replacement, make the initial hydrogen pressure 30bar, stir and react at 50°C for 24 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 85% and the enantiomeric excess was 93%. 2a: White solid, ¹ H NMR (400MHz, Chloroform-d) δ7.48 (d, J＝7.2Hz, 2H), 7.40-7.26 (m, 3H), 6.71 (d, J＝8.8Hz, 2H), 6.52(d,J＝8.8Hz,2H),5.01(s,1H),4.67(s,1H),3.70(s,3H),3.69(s,3H); ¹³ C NMR(101MHz,Chloroform-d) δ172.8,152.8,140.5,138.1,129.1,128.5,127.5,115.1,115.0,61.9,55.9,53.0.

Example 42

Preparation of 2a (Ar=PMP, R=Ph, X=O, R'=CH ₃ )

In a 10mL Schlenck tube, add phosphine ligand L7 (0.003mmol), nickel acetate tetrahydrate (0.75mg, 0.003mmol) and N-PMP-α-arylimide ester 1a (0.3mmol), and pass the system through a vacuum line , replace with nitrogen 3 times, add 1mL of DMF solvent, put it into the autoclave, after 6 times of hydrogen replacement, make the initial hydrogen pressure 30bar, stir and react at 50°C for 24 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 83% and the enantiomeric excess was 75%. 2a: White solid, ¹ H NMR (400MHz, Chloroform-d) δ7.48 (d, J＝7.2Hz, 2H), 7.40-7.26 (m, 3H), 6.71 (d, J＝8.8Hz, 2H), 6.52(d,J＝8.8Hz,2H),5.01(s,1H),4.67(s,1H),3.70(s,3H),3.69(s,3H); ¹³ C NMR(101MHz,Chloroform-d) δ172.8,152.8,140.5,138.1,129.1,128.5,127.5,115.1,115.0,61.9,55.9,53.0.

Example 43

Preparation of 2a (Ar=PMP, R=Ph, X=O, R'=CH ₃ )

In a 10mL Schlenck tube, add phosphine ligand L7 (0.003mmol), nickel acetate tetrahydrate (0.75mg, 0.003mmol) and N-PMP-α-arylimide ester 1a (0.3mmol), and pass the system through a vacuum line , replace with nitrogen 3 times, add 1 mL of toluene solvent, put into the autoclave, after 6 times of hydrogen replacement, make the initial hydrogen pressure 30bar, stir and react at 50°C for 24 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 94% and the enantiomeric excess was 89%. 2a: White solid, ¹ H NMR (400MHz, Chloroform-d) δ7.48 (d, J＝7.2Hz, 2H), 7.40-7.26 (m, 3H), 6.71 (d, J＝8.8Hz, 2H), 6.52(d,J＝8.8Hz,2H),5.01(s,1H),4.67(s,1H),3.70(s,3H),3.69(s,3H); ¹³ C NMR(101MHz,Chloroform-d) δ172.8,152.8,140.5,138.1,129.1,128.5,127.5,115.1,115.0,61.9,55.9,53.0.

Example 44

Preparation of 2a (Ar=PMP, R=Ph, X=O, R'=CH ₃ )

In a 10mL Schlenck tube, add phosphine ligand L7 (0.003mmol), nickel acetate tetrahydrate (0.75mg, 0.003mmol) and N-PMP-α-arylimide ester 1a (0.3mmol), and pass the system through a vacuum line , replace with nitrogen 3 times, add 1 mL of methylene chloride solvent, put it into the autoclave, after 6 times of hydrogen replacement, make the initial hydrogen pressure 30bar, stir and react at 50°C for 24 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 71% and the enantiomeric excess was 76%. 2a: White solid, ¹ H NMR (400MHz, Chloroform-d) δ7.48 (d, J＝7.2Hz, 2H), 7.40-7.26 (m, 3H), 6.71 (d, J＝8.8Hz, 2H), 6.52(d,J＝8.8Hz,2H),5.01(s,1H),4.67(s,1H),3.70(s,3H),3.69(s,3H); ¹³ C NMR(101MHz,Chloroform-d) δ172.8,152.8,140.5,138.1,129.1,128.5,127.5,115.1,115.0,61.9,55.9,53.0.

Example 45

Preparation of 2a (Ar=PMP, R=Ph, X=O, R'=CH ₃ )

In a 10mL Schlenck tube, add phosphine ligand L7 (0.003mmol), nickel acetate tetrahydrate (0.75mg, 0.003mmol) and N-PMP-α-arylimide ester 1a (0.3mmol), and pass the system through a vacuum line , replace with nitrogen 3 times, add 1mL trifluoroethanol/dichloromethane (2:1) solvent, put it into the autoclave, after 6 times of hydrogen replacement, make the initial hydrogen pressure 30bar, stir and react at 50°C for 24 hours . Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 86% and the enantiomeric excess was 90%. 2a: White solid, ¹ HNMR (400MHz, Chloroform-d) δ7.48 (d, J＝7.2Hz, 2H), 7.40-7.26 (m, 3H), 6.71 (d, J＝8.8Hz, 2H), 6.52 (d, J=8.8Hz, 2H), 5.01 (s, 1H), 4.67 (s, 1H), 3.70 (s, 3H), 3.69 (s, 3H); ¹³ C NMR (101MHz, Chloroform-d) δ172 .8,152.8,140.5,138.1,129.1,128.5,127.5,115.1,115.0,61.9,55.9,53.0.

Example 46

Preparation of 2a (Ar=PMP, R=Ph, X=O, R'=CH ₃ )

In a 10mL Schlenck tube, add phosphine ligand L7 (0.003mmol), nickel acetate tetrahydrate (0.75mg, 0.003mmol) and N-PMP-α-arylimide ester 1a (0.3mmol), and pass the system through a vacuum line , replace with nitrogen 3 times, add 1mL trifluoroethanol/ether (2:1) solvent, put it into the autoclave, after 6 times of hydrogen replacement, make the initial hydrogen pressure 30bar, stir and react at 50°C for 24 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 64% and the enantiomeric excess was 84%. 2a: White solid, ¹ H NMR (400MHz, Chloroform-d) δ7.48 (d, J＝7.2Hz, 2H), 7.40-7.26 (m, 3H), 6.71 (d, J＝8.8Hz, 2H), 6.52(d,J＝8.8Hz,2H),5.01(s,1H),4.67(s,1H),3.70(s,3H),3.69(s,3H); ¹³ C NMR(101MHz,Chloroform-d) δ172.8,152.8,140.5,138.1,129.1,128.5,127.5,115.1,115.0,61.9,55.9,53.0.

Example 47

Preparation of 2a (Ar=PMP, R=Ph, X=O, R'=CH ₃ )

In a 10mL Schlenck tube, add phosphine ligand L7 (0.003mmol), nickel acetate tetrahydrate (0.75mg, 0.003mmol) and N-PMP-α-arylimide ester 1a (0.3mmol), and pass the system through a vacuum line , replace with nitrogen 3 times, add 1mL trifluoroethanol/ethanol (2:1)) solvent, put it into the autoclave, after 6 times of hydrogen replacement, make the initial hydrogen pressure 30bar, stir and react at 50°C for 24 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 65% and the enantiomeric excess was 68%. 2a: White solid, ¹ H NMR (400MHz, Chloroform-d) δ7.48 (d, J＝7.2Hz, 2H), 7.40-7.26 (m, 3H), 6.71 (d, J＝8.8Hz, 2H), 6.52(d,J＝8.8Hz,2H),5.01(s,1H),4.67(s,1H),3.70(s,3H),3.69(s,3H); ¹³ C NMR(101MHz,Chloroform-d) δ172.8,152.8,140.5,138.1,129.1,128.5,127.5,115.1,115.0,61.9,55.9,53.0.

Example 48

Preparation of 2a (Ar=PMP, R=Ph, X=O, R'=CH ₃ )

In a 10mL Schlenck tube, add phosphine ligand L7 (0.003mmol), nickel acetate tetrahydrate (0.75mg, 0.003mmol) and N-PMP-α-arylimide ester 1a (0.3mmol), and pass the system through a vacuum line , replace with nitrogen 3 times, add 1mL trifluoroethanol/ethanol (1:1) solvent, put it into the autoclave, after 6 times of hydrogen replacement, make the initial hydrogen pressure 30bar, stir and react at 50°C for 24 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 77% and the enantiomeric excess was 63%. 2a: White solid, ¹ H NMR (400MHz, Chloroform-d) δ7.48 (d, J＝7.2Hz, 2H), 7.40-7.26 (m, 3H), 6.71 (d, J＝8.8Hz, 2H), 6.52(d,J＝8.8Hz,2H),5.01(s,1H),4.67(s,1H),3.70(s,3H),3.69(s,3H); ¹³ C NMR(101MHz,Chloroform-d) δ172.8,152.8,140.5,138.1,129.1,128.5,127.5,115.1,115.0,61.9,55.9,53.0.

Example 49

Preparation of 2a (Ar=PMP, R=Ph, X=O, R'=CH ₃ )

In a 10mL Schlenck tube, add phosphine ligand L7 (0.003mmol), nickel acetate tetrahydrate (0.75mg, 0.003mmol) and N-PMP-α-arylimide ester 1a (0.3mmol), and pass the system through a vacuum line , replace with nitrogen 3 times, add 1mL trifluoroethanol/ethanol (1:2) solvent, put it into the autoclave, after 6 times of hydrogen replacement, make the initial hydrogen pressure 30bar, stir and react at 50°C for 24 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 98% and the enantiomeric excess was 89%. 2a: White solid, ¹ H NMR (400MHz, Chloroform-d) δ7.48 (d, J＝7.2Hz, 2H), 7.40-7.26 (m, 3H), 6.71 (d, J＝8.8Hz, 2H), 6.52(d,J＝8.8Hz,2H),5.01(s,1H),4.67(s,1H),3.70(s,3H),3.69(s,3H); ¹³ C NMR(101MHz,Chloroform-d) δ172.8,152.8,140.5,138.1,129.1,128.5,127.5,115.1,115.0,61.9,55.9,53.0.

Example 50

Preparation of 2a (Ar=PMP, R=Ph, X=O, R'=CH ₃ )

In a 10mL Schlenck tube, add phosphine ligand L7 (0.003mmol), nickel acetate tetrahydrate (0.75mg, 0.003mmol) and N-PMP-α-arylimide ester 1a (0.3mmol), and pass the system through a vacuum line , replace with nitrogen 3 times, add 1 mL of trifluoroethanol solvent, put it into the autoclave, after 6 times of hydrogen replacement, make the initial hydrogen pressure 5bar, stir and react at 50°C for 24 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 71% and the enantiomeric excess was 92%. 2a: White solid, ¹ H NMR (400MHz, Chloroform-d) δ7.48 (d, J＝7.2Hz, 2H), 7.40-7.26 (m, 3H), 6.71 (d, J＝8.8Hz, 2H), 6.52(d,J＝8.8Hz,2H),5.01(s,1H),4.67(s,1H),3.70(s,3H),3.69(s,3H); ¹³ C NMR(101MHz,Chloroform-d) δ172.8,152.8,140.5,138.1,129.1,128.5,127.5,115.1,115.0,61.9,55.9,53.0.

Example 51

Preparation of 2a (Ar=PMP, R=Ph, X=O, R'=CH ₃ )

In a 10mL Schlenck tube, add phosphine ligand L7 (0.003mmol), nickel acetate tetrahydrate (0.75mg, 0.003mmol) and N-PMP-α-arylimide ester 1a (0.3mmol), and pass the system through a vacuum line , replace with nitrogen 3 times, add 1 mL of trifluoroethanol solvent, put it into the autoclave, after 6 times of hydrogen replacement, make the initial hydrogen pressure 10bar, stir and react at 50°C for 24 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 79% and the enantiomeric excess was 92%. 2a: White solid, ¹ H NMR (400MHz, Chloroform-d) δ7.48 (d, J＝7.2Hz, 2H), 7.40-7.26 (m, 3H), 6.71 (d, J＝8.8Hz, 2H), 6.52(d,J＝8.8Hz,2H),5.01(s,1H),4.67(s,1H),3.70(s,3H),3.69(s,3H); ¹³ C NMR(101MHz,Chloroform-d) δ172.8,152.8,140.5,138.1,129.1,128.5,127.5,115.1,115.0,61.9,55.9,53.0.

Example 52

Preparation of 2a (Ar=PMP, R=Ph, X=O, R'=CH ₃ )

In a 10mL Schlenck tube, add phosphine ligand L7 (0.003mmol), nickel acetate tetrahydrate (0.75mg, 0.003mmol) and N-PMP-α-arylimide ester 1a (0.3mmol), and pass the system through a vacuum line , replace with nitrogen 3 times, add 1 mL of trifluoroethanol solvent, put it into the autoclave, after 6 times of hydrogen replacement, make the initial hydrogen pressure 20bar, stir and react at 50°C for 24 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 85% and the enantiomeric excess was 96%. 2a: White solid, ¹ H NMR (400MHz, Chloroform-d) δ7.48 (d, J＝7.2Hz, 2H), 7.40-7.26 (m, 3H), 6.71 (d, J＝8.8Hz, 2H), 6.52(d,J＝8.8Hz,2H),5.01(s,1H),4.67(s,1H),3.70(s,3H),3.69(s,3H); ¹³ C NMR(101MHz,Chloroform-d) δ172.8,152.8,140.5,138.1,129.1,128.5,127.5,115.1,115.0,61.9,55.9,53.0.

Example 53

Preparation of 2a (Ar=PMP, R=Ph, X=O, R'=CH ₃ )

In a 10mL Schlenck tube, add phosphine ligand L7 (0.003mmol), nickel acetate tetrahydrate (0.75mg, 0.003mmol) and N-PMP-α-arylimide ester 1a (0.3mmol), and pass the system through a vacuum line , replace with nitrogen 3 times, add 1 mL of trifluoroethanol solvent, put it into the autoclave, after 6 times of hydrogen replacement, make the initial hydrogen pressure 50bar, stir and react at 50°C for 24 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 99% and the enantiomeric excess was 95%. 2a: White solid, ¹ H NMR (400MHz, Chloroform-d) δ7.48 (d, J＝7.2Hz, 2H), 7.40-7.26 (m, 3H), 6.71 (d, J＝8.8Hz, 2H), 6.52(d,J＝8.8Hz,2H),5.01(s,1H),4.67(s,1H),3.70(s,3H),3.69(s,3H); ¹³ C NMR(101MHz,Chloroform-d) δ172.8,152.8,140.5,138.1,129.1,128.5,127.5,115.1,115.0,61.9,55.9,53.0.

Example 54

Preparation of 2a (Ar=PMP, R=Ph, X=O, R'=CH ₃ )

In a 10mL Schlenck tube, add phosphine ligand L7 (0.003mmol), nickel acetate tetrahydrate (0.75mg, 0.003mmol) and N-PMP-α-arylimide ester 1a (0.3mmol), and pass the system through a vacuum line , replace with nitrogen 3 times, add 1 mL of trifluoroethanol solvent, put it into the autoclave, after 6 times of hydrogen replacement, make the initial hydrogen pressure 100bar, stir and react at 50°C for 24 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 99% and the enantiomeric excess was 92%. 2a: White solid, ¹ H NMR (400MHz, Chloroform-d) δ7.48 (d, J＝7.2Hz, 2H), 7.40-7.26 (m, 3H), 6.71 (d, J＝8.8Hz, 2H), 6.52(d,J＝8.8Hz,2H),5.01(s,1H),4.67(s,1H),3.70(s,3H),3.69(s,3H); ¹³ C NMR(101MHz,Chloroform-d) δ172.8,152.8,140.5,138.1,129.1,128.5,127.5,115.1,115.0,61.9,55.9,53.0.

Example 55

Preparation of 2a (Ar=PMP, R=Ph, X=O, R'=CH ₃ )

In a 10mL Schlenck tube, add phosphine ligand L7 (0.003mmol), nickel acetate tetrahydrate (0.75mg, 0.003mmol) and N-PMP-α-arylimide ester 1a (0.3mmol), and pass the system through a vacuum line , replace with nitrogen 3 times, add 1 mL of trifluoroethanol solvent, put it into the autoclave, after 6 times of hydrogen replacement, make the initial hydrogen pressure 30bar, stir and react at 25°C for 24 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 94% and the enantiomeric excess was 96%. 2a: White solid, ¹ H NMR (400MHz, Chloroform-d) δ7.48 (d, J＝7.2Hz, 2H), 7.40-7.26 (m, 3H), 6.71 (d, J＝8.8Hz, 2H), 6.52(d,J＝8.8Hz,2H),5.01(s,1H),4.67(s,1H),3.70(s,3H),3.69(s,3H); ¹³ C NMR(101MHz,Chloroform-d) δ172.8,152.8,140.5,138.1,129.1,128.5,127.5,115.1,115.0,61.9,55.9,53.0.

Example 56

Preparation of 2a (Ar=PMP, R=Ph, X=O, R'=CH ₃ )

In a 10mL Schlenck tube, add phosphine ligand L7 (0.003mmol), nickel acetate tetrahydrate (0.75mg, 0.003mmol) and N-PMP-α-arylimide ester 1a (0.3mmol), and pass the system through a vacuum line , replace with nitrogen 3 times, add 1 mL of trifluoroethanol solvent, put it into the autoclave, after 6 times of hydrogen replacement, make the initial hydrogen pressure 30bar, stir and react at 70°C for 24 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 99% and the enantiomeric excess was 94%. 2a: White solid, ¹ H NMR (400MHz, Chloroform-d) δ7.48 (d, J＝7.2Hz, 2H), 7.40-7.26 (m, 3H), 6.71 (d, J＝8.8Hz, 2H), 6.52(d,J＝8.8Hz,2H),5.01(s,1H),4.67(s,1H),3.70(s,3H),3.69(s,3H); ¹³ C NMR(101MHz,Chloroform-d) δ172.8,152.8,140.5,138.1,129.1,128.5,127.5,115.1,115.0,61.9,55.9,53.0.

Example 57

Preparation of 2a (Ar=PMP, R=Ph, X=O, R'=CH ₃ )

In a 10mL Schlenck tube, add phosphine ligand L7 (0.003mmol), nickel acetate tetrahydrate (0.75mg, 0.003mmol) and N-PMP-α-arylimide ester 1a (0.3mmol), and pass the system through a vacuum line , replace with nitrogen 3 times, add 1 mL of trifluoroethanol solvent, put it into the autoclave, after 6 times of hydrogen replacement, make the initial hydrogen pressure 30bar, stir and react at 100°C for 24 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 99% and the enantiomeric excess was 90%. 2a: White solid, ¹ H NMR (400MHz, Chloroform-d) δ7.48 (d, J＝7.2Hz, 2H), 7.40-7.26 (m, 3H), 6.71 (d, J＝8.8Hz, 2H), 6.52(d,J＝8.8Hz,2H),5.01(s,1H),4.67(s,1H),3.70(s,3H),3.69(s,3H); ¹³ C NMR(101MHz,Chloroform-d) δ172.8,152.8,140.5,138.1,129.1,128.5,127.5,115.1,115.0,61.9,55.9,53.0.

Example 58

Preparation of 2a (Ar=PMP, R=Ph, X=O, R'=CH ₃ )

In a 10mL Schlenck tube, add phosphine ligand L7 (0.003mmol), nickel acetate tetrahydrate (0.75mg, 0.003mmol) and N-PMP-α-arylimide ester 1a (0.3mmol), and pass the system through a vacuum line , replace with nitrogen 3 times, add 1 mL of trifluoroethanol solvent, put it into the autoclave, after 6 times of hydrogen replacement, make the initial hydrogen pressure 30bar, stir and react at 50°C for 12 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 90% and the enantiomeric excess was 97%. 2a: White solid, ¹ H NMR (400MHz, Chloroform-d) δ7.48 (d, J＝7.2Hz, 2H), 7.40-7.26 (m, 3H), 6.71 (d, J＝8.8Hz, 2H), 6.52(d,J＝8.8Hz,2H),5.01(s,1H),4.67(s,1H),3.70(s,3H),3.69(s,3H); ¹³ C NMR(101MHz,Chloroform-d) δ172.8,152.8,140.5,138.1,129.1,128.5,127.5,115.1,115.0,61.9,55.9,53.0.

Example 59

Preparation of 2a (Ar=PMP, R=Ph, X=O, R'=CH ₃ )

In a 10mL Schlenck tube, add phosphine ligand L7 (0.003mmol), nickel acetate tetrahydrate (0.75mg, 0.003mmol) and N-PMP-α-arylimide ester 1a (0.3mmol), and pass the system through a vacuum line , replace with nitrogen 3 times, add 1 mL of trifluoroethanol solvent, put it into the autoclave, after 6 times of hydrogen replacement, make the initial hydrogen pressure 30bar, stir and react at 50°C for 48 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 99% and the enantiomeric excess was 96%. 2a: White solid, ¹ H NMR (400MHz, Chloroform-d) δ7.48 (d, J＝7.2Hz, 2H), 7.40-7.26 (m, 3H), 6.71 (d, J＝8.8Hz, 2H), 6.52(d,J＝8.8Hz,2H),5.01(s,1H),4.67(s,1H),3.70(s,3H),3.69(s,3H); ¹³ C NMR(101MHz,Chloroform-d) δ172.8,152.8,140.5,138.1,129.1,128.5,127.5,115.1,115.0,61.9,55.9,53.0.

Example 60

Preparation of 2a (Ar=PMP, R=Ph, X=O, R'=CH ₃ )

In a 10mL Schlenck tube, add phosphine ligand L7 (0.003mmol), nickel acetate tetrahydrate (0.75mg, 0.003mmol) and N-PMP-α-arylimide ester 1a (1.2mmol, S/C=400 ), the system passed through the vacuum line, replaced with nitrogen 3 times, added 1 mL of trifluoroethanol solvent, and put it into the autoclave. After 6 times of hydrogen replacement, the initial hydrogen pressure was set to 30 bar, and the reaction was stirred at 50°C for 24 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 99% and the enantiomeric excess was 96%. 2a: White solid, ¹ H NMR (400MHz, Chloroform-d) δ7.48 (d, J＝7.2Hz, 2H), 7.40-7.26 (m, 3H), 6.71 (d, J＝8.8Hz, 2H), 6.52(d,J＝8.8Hz,2H),5.01(s,1H),4.67(s,1H),3.70(s,3H),3.69(s,3H); ¹³ C NMR(101MHz,Chloroform-d) δ172.8,152.8,140.5,138.1,129.1,128.5,127.5,115.1,115.0,61.9,55.9,53.0.

Example 61

Preparation of 2a (Ar=PMP, R=Ph, X=O, R'=CH ₃ )

In a 10mL Schlenck tube, add phosphine ligand L7 (0.003mmol), nickel acetate tetrahydrate (0.75mg, 0.03mmol) and N-PMP-α-arylimide ester 1a (3mmol, S/C=1000) , the system passed through the vacuum line, replaced with nitrogen three times, added 1 mL of trifluoroethanol solvent, and put it into the autoclave. After 6 hydrogen replacements, the initial hydrogen pressure was set to 30 bar, and the reaction was stirred at 50°C for 24 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 96% and the enantiomeric excess was 96%. 2a: White solid, ¹ H NMR (400MHz, Chloroform-d) δ7.48 (d, J＝7.2Hz, 2H), 7.40-7.26 (m, 3H), 6.71 (d, J＝8.8Hz, 2H), 6.52(d,J＝8.8Hz,2H),5.01(s,1H),4.67(s,1H),3.70(s,3H),3.69(s,3H); ¹³ C NMR(101MHz,Chloroform-d) δ172.8,152.8,140.5,138.1,129.1,128.5,127.5,115.1,115.0,61.9,55.9,53.0.

Example 62

Preparation of 2a (Ar=PMP, R=Ph, X=O, R'=CH ₃ )

In a 10mL Schlenck tube, add phosphine ligand L7 (0.003mmol), nickel acetate tetrahydrate (0.75mg, 0.06mmol) and N-PMP-α-arylimide ester 1a (6mmol, S/C=2000) , the system passed through the vacuum line, replaced with nitrogen three times, added 1 mL of trifluoroethanol solvent, and put it into the autoclave. After 6 hydrogen replacements, the initial hydrogen pressure was set to 30 bar, and the reaction was stirred at 50°C for 24 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 94% and the enantiomeric excess was 96%. 2a: White solid, ¹ H NMR (400MHz, Chloroform-d) δ7.48 (d, J＝7.2Hz, 2H), 7.40-7.26 (m, 3H), 6.71 (d, J＝8.8Hz, 2H), 6.52(d,J＝8.8Hz,2H),5.01(s,1H),4.67(s,1H),3.70(s,3H),3.69(s,3H); ¹³ C NMR(101MHz,Chloroform-d) δ172.8,152.8,140.5,138.1,129.1,128.5,127.5,115.1,115.0,61.9,55.9,53.0.

Example 63

Preparation of 2a (Ar=PMP, R=Ph, X=O, R'=CH ₃ )

In a 10mL Schlenck tube, add phosphine ligand L7 (0.003mmol), nickel acetate tetrahydrate (0.75mg, 0.06mmol) and N-PMP-α-arylimide ester 1a (15mmol, S/C=5000) , the system passed through the vacuum line, replaced with nitrogen three times, added 1 mL of trifluoroethanol solvent, and put it into the autoclave. After 6 hydrogen replacements, the initial hydrogen pressure was set to 30 bar, and the reaction was stirred at 50°C for 24 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 92% and the enantiomeric excess was 96%. 2a: White solid, ¹ H NMR (400MHz, Chloroform-d) δ7.48 (d, J＝7.2Hz, 2H), 7.40-7.26 (m, 3H), 6.71 (d, J＝8.8Hz, 2H), 6.52(d,J＝8.8Hz,2H),5.01(s,1H),4.67(s,1H),3.70(s,3H),3.69(s,3H); ¹³ C NMR(101MHz,Chloroform-d) δ172.8,152.8,140.5,138.1,129.1,128.5,127.5,115.1,115.0,61.9,55.9,53.0.

Example 64

Preparation of 2a (Ar=PMP, R=Ph, X=O, R'=CH ₃ )

In a 10mL Schlenck tube, add phosphine ligand L7 (0.003mmol), nickel acetate tetrahydrate (0.75mg, 0.06mmol) and N-PMP-α-arylimide ester 1a (24mmol, S/C=8000) , the system passed through the vacuum line, replaced with nitrogen three times, added 1 mL of trifluoroethanol solvent, and put it into the autoclave. After 6 hydrogen replacements, the initial hydrogen pressure was set to 30 bar, and the reaction was stirred at 50°C for 24 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 87% and the enantiomeric excess was 95%. 2a: White solid, ¹ H NMR (400MHz, Chloroform-d) δ7.48 (d, J＝7.2Hz, 2H), 7.40-7.26 (m, 3H), 6.71 (d, J＝8.8Hz, 2H), 6.52(d,J＝8.8Hz,2H),5.01(s,1H),4.67(s,1H),3.70(s,3H),3.69(s,3H); ¹³ C NMR(101MHz,Chloroform-d) δ172.8,152.8,140.5,138.1,129.1,128.5,127.5,115.1,115.0,61.9,55.9,53.0.

Example 65

Preparation of 2a (Ar=PMP, R=Ph, X=O, R'=CH ₃ )

In a 10mL Schlenck tube, add phosphine ligand L7 (0.003mmol), nickel acetate tetrahydrate (0.75mg, 0.06mmol) and N-PMP-α-arylimide ester 1a (30mmol, S/C=1000) , the system passed through the vacuum line, replaced with nitrogen three times, added 1 mL of trifluoroethanol solvent, and put it into the autoclave. After 6 hydrogen replacements, the initial hydrogen pressure was set to 30 bar, and the reaction was stirred at 50°C for 24 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 82% and the enantiomeric excess was 94%. 2a: White solid, ¹ H NMR (400MHz, Chloroform-d) δ7.48 (d, J＝7.2Hz, 2H), 7.40-7.26 (m, 3H), 6.71 (d, J＝8.8Hz, 2H), 6.52(d,J＝8.8Hz,2H),5.01(s,1H),4.67(s,1H),3.70(s,3H),3.69(s,3H); ¹³ C NMR(101MHz,Chloroform-d) δ172.8,152.8,140.5,138.1,129.1,128.5,127.5,115.1,115.0,61.9,55.9,53.0.

Example 66

Preparation of 2a (Ar=PMP, R=Ph, X=O, R'=CH ₃ )

In a 10mL Schlenck tube, add phosphine ligand L7 (0.004mmol), nickel acetate tetrahydrate (0.99mg, 0.004mmol) and N-PMP-α-arylimide ester 1a (8mmol), and pass the system through a vacuum line. Replace with nitrogen 3 times, add 9 mL of trifluoroethanol solvent, and put it into the autoclave. After 6 hydrogen replacements, make the initial hydrogen pressure 50 bar and stir the reaction at 70°C for 48 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 99% and the enantiomeric excess was 96%. 2a: White solid, ¹ H NMR (400MHz, Chloroform-d) δ7.48 (d, J＝7.2Hz, 2H), 7.40-7.26 (m, 3H), 6.71 (d, J＝8.8Hz, 2H), 6.52(d,J＝8.8Hz,2H),5.01(s,1H),4.67(s,1H),3.70(s,3H),3.69(s,3H); ¹³ C NMR(101MHz,Chloroform-d) δ172.8,152.8,140.5,138.1,129.1,128.5,127.5,115.1,115.0,61.9,55.9,53.0.

Example 67

Preparation of 2b (Ar=PMP, R=2-F-Ph, X=O, R'=CH ₃ )

In a 10mL Schlenck tube, add phosphine ligand L7 (0.003mmol), nickel acetate tetrahydrate (0.75mg, 0.003mmol) and N-PMP-α-arylimide ester 1b (0.3mmol), and pass the system through a vacuum line , replace with nitrogen 3 times, add 1 mL of trifluoroethanol solvent, put it into the autoclave, after 6 times of hydrogen replacement, make the initial hydrogen pressure 30bar, stir and react at 50°C for 24 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 99% and the enantiomeric excess was 98%. 2b: Colorless liquid, ¹ H NMRδ7.42(td,J＝7.6Hz,2.0Hz,1H),7.31-7.24(m,1H),7.14-7.05(m,2H),6.72(d,J＝8.8 Hz, 2H), 6.56 (d, J = 8.8Hz, 2H), 5.38 (s, 1H), 4.76 (s, 1H), 3.71 (s, 3H), 3.69 (s, 3H); ¹³ C NMR (101MHz ,Chloroform-d)δ172.0,160.8(d,J＝248.5Hz),152.7,139.8,129.9(d,J＝8.3Hz),128.3(d,J＝3.5Hz),125.4(d,J＝13.8Hz) ,124.7(d,J＝3.4Hz),115.8(d,J＝21.8Hz),114.9,55.7,54.7(d,J＝3.0Hz),52.9; ¹⁹ F NMR(376MHz,Chloroform-d)δ-118.48 .

Example 68

Preparation of 2c (Ar=PMP, R=2-Cl-Ph, X=O, R'=CH ₃ )

In a 10mL Schlenck tube, add phosphine ligand L7 (0.003mmol), nickel acetate (0.75mg, 0.003mmol) and N-PMP-α-arylimide ester 1c (0.3mmol), and pass the system through a vacuum line with Replace with nitrogen 3 times, add 1 mL of trifluoroethanol solvent, and put it into the autoclave. After 6 times of hydrogen replacement, make the initial hydrogen pressure 30 bar and stir the reaction at 50°C for 24 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 98% and the enantiomeric excess was 96%. 2c: Colorless liquid, ¹ H NMR (400MHz, Chloroform-d) δ7.46-7.44(m,1H),7.41-7.39(m,1H),7.23-7.20(m,2H),6.71(d,J ＝8.8Hz,2H),6.53(d,J＝8.8Hz,2H),5.54(s,1H),4.79(s,1H),3.70(s,3H),3.68(s,3H); ¹³ CNMR( 101MHz,Chloroform-d)δ172.3,152.9,140.1,136.1,134.4,130.2,129.6,128.5,127.7,115.1,115.0,58.2,55.9,53.1.

Example 69

Preparation of 2d (Ar=PMP, R=2-Br-Ph, X=O, R'=CH ₃ )

In a 10mL Schlenck tube, add phosphine ligand L7 (0.003mmol), nickel acetate tetrahydrate (0.75mg, 0.003mmol) and N-PMP-α-arylimide ester 1d (0.3mmol), and pass the system through a vacuum line , replace with nitrogen 3 times, add 1 mL of trifluoroethanol solvent, put it into the autoclave, after 6 times of hydrogen replacement, make the initial hydrogen pressure 30bar, stir and react at 50°C for 24 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 98% and the enantiomeric excess was 94%. 2d: Colorless liquid, ¹ H NMR (400MHz, Chloroform-d) δ7.59 (dd, J＝8.0Hz, 1.6Hz, 1H), 7.45 (dd, J＝8.0Hz, 1.6Hz, 1H), 7.28- 7.24(m,1H),7.16-7.12(m,1H),6.71(d,J＝8.8Hz,2H),6.53(d,J＝8.8Hz,2H),5.53(s,1H),4.81(s ,1H),3.71(s,3H),3.68(s,3H); ¹³ C NMR(101MHz,Chloroform-d)δ172.0,152.7,139.8,137.5,133.3,129.7,128.4,128.1,124.6,114.9,60.4, 55.7,52.9.

Example 70

Preparation of 2e (Ar=PMP, R=2-CF ₃ -Ph, X=O, R'=CH ₃ )

In a 10mL Schlenck tube, add phosphine ligand L7 (0.003mmol), nickel acetate tetrahydrate (0.75mg, 0.003mmol) and N-PMP-α-arylimide ester 1e (0.3mmol), and pass the system through a vacuum line , replace with nitrogen 3 times, add 1 mL of trifluoroethanol solvent, put it into the autoclave, after 6 times of hydrogen replacement, make the initial hydrogen pressure 30bar, stir and react at 50°C for 24 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 97% and the enantiomeric excess was 92%. 2e: Colorless liquid, ¹ H NMR (400MHz, Chloroform-d) δ7.70 (t, J = 8.8Hz, 2H), 7.52 (t, J = 7.2Hz, 1H), 7.41 (t, J = 8.0Hz ,1H),6.72(d,J＝8.8Hz,2H),6.60(d,J＝8.8Hz,2H),5.46(s,1H),4.54(s,1H),3.69(s,6H); ¹³ CNMR(101MHz,Chloroform-d)δ172.3,153.1,140.0,136.7(d,J＝2.0Hz),132.6,128.8(q,J＝30.3Hz),128.5,128.4,126.6(q,J＝5.1Hz), 124.3 (q, J=275.7Hz), 115.5, 114.8, 57.8 (q, J=4.0Hz), 55.6, 52.9; ¹⁹ F NMR (376MHz, Chloroform-d) δ-58.06.

Example 71

Preparation of 2f (Ar=PMP, R=2-Me-Ph, X=O, R'=CH ₃ )

In a 10mL Schlenck tube, add phosphine ligand L7 (0.003mmol), nickel acetate tetrahydrate (0.75mg, 0.003mmol) and N-PMP-α-arylimide ester 1f (0.3mmol), and pass the system through a vacuum line , replace with nitrogen 3 times, add 1 mL of trifluoroethanol solvent, put it into the autoclave, after 6 times of hydrogen replacement, make the initial hydrogen pressure 30bar, stir and react at 50°C for 24 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 97% and the enantiomeric excess was 98%. 2f: Colorless liquid, ¹ H NMR (400MHz, Chloroform-d) δ7.38 (d, J＝6.8Hz, 1H), 7.21-7.13 (m, 3H), 6.71 (d, J＝8.8Hz, 2H) ¹³ C NMR (101MHz, Chloroform-d) δ173.0,152.6,140.5,136.7,136.1,131.0,128.2,126.7,126.5,114.9,114.6,58.3,55.7,52.6,19.6.

Example 72

Preparation of 2g (Ar=PMP, R=2-MeOPh, X=O, R'=CH ₃ )

In a 10mL Schlenck tube, add phosphine ligand L7 (0.003mmol), nickel acetate tetrahydrate (0.75mg, 0.003mmol) and N-PMP-α-arylimide ester 1g (0.3mmol), and the system passes through the vacuum line , replace with nitrogen 3 times, add 1 mL of trifluoroethanol solvent, put it into the autoclave, after 6 times of hydrogen replacement, make the initial hydrogen pressure 30bar, stir and react at 50°C for 24 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 99% and the enantiomeric excess was 97%. 2g: colorless liquid, ¹ H NMR (400MHz, Chloroform-d) δ7.33 (d, J = 9.2Hz, 1H), 7.28-7.21 (m, 1H), 6.93-6.89 (m, 2H), 6.71 ( d,J＝8.8Hz,2H),6.59(d,J＝8.8Hz,2H),5.44(s,1H),4.61(s,1H),3.88(s,3H),3.68(s,3H), 3.67 (s, 3H); ¹³ C NMR (101MHz, Chloroform-d) δ 173.3, 157.4, 152.8, 140.9, 129.7, 128.4, 126.7, 121.3, 115.3, 115.0, 111.4, 56.1, 56.0, 55.9, 52.8.

Example 73

Preparation of 2h (Ar=PMP, R=3-F-Ph, X=O, R'=CH ₃ )

In a 10mL Schlenck tube, add phosphine ligand L7 (0.003mmol), nickel acetate tetrahydrate (0.75mg, 0.003mmol) and N-PMP-α-arylimide ester for 1h (0.3mmol), and the system is passed through the vacuum line , replace with nitrogen 3 times, add 1 mL of trifluoroethanol solvent, put it into the autoclave, after 6 times of hydrogen replacement, make the initial hydrogen pressure 30bar, stir and react at 50°C for 24 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 95% and the enantiomeric excess was 98%. 2h: Colorless liquid, ¹ H NMR (400MHz, Chloroform-d) δ7.48-7.30(m,2H),7.28-7.26(m,1H),7.05-7.00(m,1H),6.77(d,J ＝8.8Hz,2H),6.56(d,J＝8.8Hz,2H),5.06(s,1H),4.77(s,1H),3.76(s,3H),3.74(s,3H); ¹³ CNMR( 101MHz,Chloroform-d)δ172.2,163.4(d,J＝247.5Hz),153.0,140.8(d,J＝6.7Hz),140.2,130.6(d,J＝8.9Hz),123.2,115.5(d,J＝ 21.2Hz), 115.2, 115.1, 114.5 (d, J = 22.2Hz), 61.5, 55.9, 53.0; ¹⁹ F NMR (376MHz, Chloroform-d) δ-112.64.

Example 74

Preparation of 2i (Ar=PMP, R=3-Cl-Ph, X=O, R'=CH ₃ )

In a 10mL Schlenck tube, add phosphine ligand L7 (0.003mmol), nickel acetate tetrahydrate (0.75mg, 0.003mmol) and N-PMP-α-arylimide ester 1i (0.3mmol), and pass the system through a vacuum line , replace with nitrogen 3 times, add 1 mL of trifluoroethanol solvent, put it into the autoclave, after 6 times of hydrogen replacement, make the initial hydrogen pressure 30bar, stir and react at 50°C for 24 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 99% and the enantiomeric excess was 97%. 2i: Colorless liquid, ¹ H NMR (400MHz, Chloroform-d) δ7.50 (s, 1H), 7.40-7.35 (m, 1H), 7.29-7.27 (m, 2H), 6.72 (d, J＝9.2 Hz, 2H), 6.50 (d, J = 9.2Hz, 2H), 4.97 (s, 1H), 4.72 (s, 1H), 3.73 (s, 3H), 3.70 (s, 3H); ¹³ C NMR (101MHz ,Chloroform-d)δ172.1,152.9,140.3,140.0,135.0,130.3,128.7,127.7,125.7,115.1,115.0,61.4,55.9,53.2.

Example 75

Preparation of 2j (Ar=PMP, R=3-Br-Ph, X=O, R'=CH ₃ )

In a 10mL Schlenck tube, add phosphine ligand L7 (0.003mmol), nickel acetate tetrahydrate (0.75mg, 0.003mmol) and N-PMP-α-arylimide ester 1j (0.3mmol), and pass the system through a vacuum line , replace with nitrogen 3 times, add 1 mL of trifluoroethanol solvent, put it into the autoclave, after 6 times of hydrogen replacement, make the initial hydrogen pressure 30bar, stir and react at 50°C for 24 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 97% and the enantiomeric excess was 97%. 2j: Colorless liquid, ¹ H NMR (400MHz, Chloroform-d) δ7.65 (t, J＝2.0Hz, 1H), 7.42-7.41 (m, 2H), 7.20 (t, J＝8.0Hz, 1H) ,6.71(d,J＝9.2Hz,2H),6.50(d,J＝9.2Hz,2H),4.96(s,1H),4.73(s,1H),3.72(s,3H),3.69(s, 3H); ¹³ C NMR (101MHz, Chloroform-d) δ 171.9, 152.7, 140.4, 139.8, 131.5, 130.4, 130.4, 126.0, 123.0, 114.9, 114.8, 61.1, 55.7, 53.0.

Example 76

Preparation of 2k (Ar=PMP, R=3-NO ₂ -Ph, X=O, R'=CH ₃ )

In a 10mL Schlenck tube, add phosphine ligand L7 (0.003mmol), nickel acetate tetrahydrate (0.75mg, 0.003mmol) and N-PMP-α-arylimide ester 1k (0.3mmol), and pass the system through a vacuum line , replace with nitrogen 3 times, add 1 mL of trifluoroethanol solvent, put it into the autoclave, after 6 times of hydrogen replacement, make the initial hydrogen pressure 30bar, stir and react at 70°C for 24 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 83% and the enantiomeric excess was 90%. 2k: Colorless liquid, ¹ H NMR (400MHz, Chloroform-d) δ8.38 (t, J = 2.0Hz, 1H), 8.15 (d, J = 8.4Hz, 1H), 7.85 (d, J = 8.0Hz ,1H),7.52(t,J＝8.0Hz,1H),6.71(d,J＝8.8Hz,2H),6.50(d,J＝8.8Hz,2H),5.12(s,1H),4.86(s ,1H),3.75(s,3H),3.69(s,3H); ¹³ C NMR(101MHz,Chloroform-d)δ171.4,153.2,148.9,140.7,139.6,133.5,130.0,123.5,122.7,115.2,115.15, 61.3,55.9,53.4.

Example 77

Preparation of 2l (Ar=PMP, R=3-Me-Ph, X=O, R'=CH ₃ )

In a 10mL Schlenck tube, add phosphine ligand L7 (0.003mmol), nickel acetate tetrahydrate (0.75mg, 0.003mmol) and N-PMP-α-arylimide ester 1l (0.3mmol), and the system passes through the vacuum line , replace with nitrogen 3 times, add 1 mL of trifluoroethanol solvent, put it into the autoclave, after 6 times of hydrogen replacement, make the initial hydrogen pressure 30bar, stir and react at 50°C for 24 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 98% and the enantiomeric excess was 96%. 2l: Colorless liquid, ¹ H NMR (400MHz, Chloroform-d) δ7.28-7.21 (m, 3H), 7.11 (d, J = 6.8Hz, 1H), 6.72 (d, J = 8.8Hz, 2H) ¹³ C NMR (101MHz, Chloroform-d) δ172.7,152.5,140.4,138.6,137.8,129.1,128.8,127.9,124.5,114.9,114.8,61.7,55.7,52.7,21.5.

Example 78

Preparation of 2m (Ar=PMP, R=3-MeO-Ph, X=O, R'=CH ₃ )

In a 10mL Schlenck tube, add phosphine ligand L7 (0.003mmol), nickel acetate tetrahydrate (0.75mg, 0.003mmol) and N-PMP-α-arylimide ester 1m (0.3mmol), and the system is passed through the vacuum line , replace with nitrogen 3 times, add 1 mL of trifluoroethanol solvent, put it into the autoclave, after 6 times of hydrogen replacement, make the initial hydrogen pressure 30bar, stir and react at 50°C for 24 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 97% and the enantiomeric excess was 96%. 2m: colorless liquid, ¹ H NMR (400MHz, Chloroform-d) δ7.26-7.22 (m, 1H), 7.07-7.03 (m, 2H), 6.82 (dd, J = 8.4Hz, 1.6Hz, 1H) ,6.70(d,J＝8.8Hz,2H),6.52(d,J＝8.8Hz,2H),4.97(s,1H),4.67(s,1H),3.76(s,3H),3.69(s, 3H), 3.68 (s, 3H); ¹³ C NMR (101MHz, Chloroform-d) δ 172.5, 160.0, 152.6, 140.2, 139.5, 129.9, 119.7, 114.9, 114.8, 113.7, 112.9, 61.7, 55.7, 55.3, 52.8.

Example 79

Preparation of 2n (Ar=PMP, R=4-F-Ph, X=O, R'=CH ₃ )

In a 10mL Schlenck tube, add phosphine ligand L7 (0.003mmol), nickel acetate tetrahydrate (0.75mg, 0.003mmol) and N-PMP-α-arylimide ester 1n (0.3mmol), and pass the system through a vacuum line , replace with nitrogen 3 times, add 1 mL of trifluoroethanol solvent, put it into the autoclave, after 6 times of hydrogen replacement, make the initial hydrogen pressure 30bar, stir and react at 50°C for 24 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 95% and the enantiomeric excess was 96%. 2n: Colorless liquid, ¹ H NMR (400MHz, Chloroform-d) δ7.47-7.44 (m, 2H), 7.03 (t, J = 8.8Hz, 2H), 6.71 (d, J = 8.8Hz, 2H) ,6.50(d,J＝8.8Hz,2H),4.99(d,J＝3.6Hz,1H),4.69(s,1H),3.71(s,3H),3.69(s,3H); ¹³ C NMR( 101MHz,Chloroform-d)δ172.3,162.6(d,J＝247.5Hz),152.6,139.9,133.6(d,J＝3.0Hz),129.0(d,J＝9.1Hz),115.8(d,J＝21.2Hz ), 114.9, 114.8, 60.9, 55.7, 52.8; ¹⁹ F NMR (376MHz, Chloroform-d) δ-113.93.

Example 80

Preparation of 2o(Ar=PMP, R=4-Cl-Ph, X=O, R'=CH ₃ )

In a 10mL Schlenck tube, add phosphine ligand L7 (0.003mmol), nickel acetate tetrahydrate (0.75mg, 0.003mmol) and N-PMP-α-arylimide ester 1o (0.3mmol), and pass the system through a vacuum line , replace with nitrogen 3 times, add 1 mL of trifluoroethanol solvent, put it into the autoclave, after 6 times of hydrogen replacement, make the initial hydrogen pressure 30bar, stir and react at 50°C for 24 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 99% and the enantiomeric excess was 97%. 2o: Colorless liquid, ¹ H NMR (400MHz, Chloroform-d) δ7.42 (d, J = 8.4Hz, 2H), 7.31 (d, J = 8.4Hz, 2H), 6.71 (d, J = 8.8Hz ,2H),6.49(d,J＝8.8Hz,2H),4.98(s,1H),4.70(s,1H),3.71(s,3H),3.69(s,3H); ¹³ C NMR(101MHz, Chloroform-d)δ172.1,152.6,139.8,136.4,134.1,129.0,128.7,114.9,114.8,61.0,55.7,52.9.

Example 81

Preparation of 2p (Ar=PMP, R=4-Br-Ph, X=O, R'=CH ₃ )

In a 10mL Schlenck tube, add phosphine ligand L7 (0.003mmol), nickel acetate tetrahydrate (0.75mg, 0.003mmol) and N-PMP-α-arylimide ester 1p (0.3mmol), and pass the system through a vacuum line , replace with nitrogen 3 times, add 1 mL of trifluoroethanol solvent, put it into the autoclave, after 6 times of hydrogen replacement, make the initial hydrogen pressure 30bar, stir and react at 50°C for 24 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 98% and the enantiomeric excess was 95%. 2p: Colorless liquid, ¹ H NMR (400MHz, Chloroform-d) δδ7.46 (d, J＝8.8Hz, 2H), 7.36 (d, J＝8.8Hz, 2H), 6.70 (d, J＝8.8Hz ,2H),6.48(d,J=8.8Hz,2H),4.96(s,1H),4.72(s,1H),3.70(s,3H),3.68(s,3H); ¹³ C NMR(101MHz, Chloroform-d)δ172.0,152.7,139.8,137.0,132.0,129.0,122.3,114.9,114.8,61.0,55.7,52.9.

Example 82

Preparation of 2q (Ar=PMP, R=4-CF ₃ -Ph, X=O, R'=CH ₃ )

In a 10mL Schlenck tube, add phosphine ligand L7 (0.003mmol), nickel acetate tetrahydrate (0.75mg, 0.003mmol) and N-PMP-α-arylimide ester 1q (0.3mmol), and pass the system through a vacuum line , replace with nitrogen 3 times, add 1 mL of trifluoroethanol solvent, put it into the autoclave, after 6 times of hydrogen replacement, make the initial hydrogen pressure 30bar, stir and react at 50°C for 24 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 96% and the enantiomeric excess was 97%. 2q: Colorless liquid, ¹ H NMR (400MHz, Chloroform-d) δ7.64-7.59 (m, 4H), 6.72 (d, J = 8.8Hz, 2H), 6.49 (d, J = 8.8Hz, 2H) ,5.07(s,1H),4.78(s,1H),3.73(s,3H),3.69(s,3H); ¹³ C NMR(101MHz,Chloroform-d)δ171.7,152.7,142.0(d,J＝1.0 ¹⁹ F NMR (376MHz,Chloroform-d)δ-62.73.

Example 83

Preparation of 2r (Ar=PMP, R=4-Me-Ph, X=O, R'=CH ₃ )

In a 10mL Schlenck tube, add phosphine ligand L7 (0.003mmol), nickel acetate tetrahydrate (0.75mg, 0.003mmol) and N-PMP-α-arylimide ester 1r (0.3mmol), and pass the system through a vacuum line , replace with nitrogen 3 times, add 1 mL of trifluoroethanol solvent, put it into the autoclave, after 6 times of hydrogen replacement, make the initial hydrogen pressure 30bar, stir and react at 50°C for 24 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 99% and the enantiomeric excess was 96%. 2r: Colorless liquid, ¹ H NMR (400MHz, Chloroform-d) δ7.35 (d, J = 8.0Hz, 2H), 7.14 (d, J = 8.0Hz, 2H), 6.70 (d, J = 8.8Hz ,2H),6.52(d,J＝8.8Hz,2H),4.98(s,1H),4.64(s,1H),3.69(s,3H),3.68(s,3H),2.31(s,3H) ; ¹³ CNMR(101MHz,Chloroform-d)δ172.8,152.5,140.3,138.1,134.8,129.6,127.2,114.9,114.8,61.4,55.7,52.7,21.2.

Example 84

Preparation of 2s (Ar=PMP, R=4-MeO-Ph, X=O, R'=CH ₃ )

In a 10mL Schlenck tube, add phosphine ligand L7 (0.003mmol), nickel acetate tetrahydrate (0.75mg, 0.003mmol) and N-PMP-α-arylimide ester 1s (0.3mmol), and the system is passed through the vacuum line , replace with nitrogen 3 times, add 1 mL of trifluoroethanol solvent, put it into the autoclave, after 6 times of hydrogen replacement, make the initial hydrogen pressure 30bar, stir and react at 50°C for 24 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 95% and the enantiomeric excess was 94%. 2s: Colorless liquid, ¹ H NMR (400MHz, Chloroform-d) δ7.38 (d, J＝8.8Hz, 2H), 6.86 (d, J＝8.8Hz, 2H), 6.71 (d, J＝8.8Hz ,2H),6.52(d,J＝8.8Hz,2H),4.96(s,1H),4.62(s,1H),3.75(s,3H),3.69(s,3H),3.68(s,3H) ; ¹³ CNMR (101MHz, Chloroform-d) δ 172.8, 159.6, 152.5, 140.3, 129.8, 128.5, 114.9, 114.8, 114.3, 61.0, 55.7, 55.3, 52.7.

Example 85

Preparation of 2t (Ar=PMP, R=4-Ph-Ph, X=O, R'=CH ₃ )

In a 10mL Schlenck tube, add phosphine ligand L7 (0.003mmol), nickel acetate tetrahydrate (0.75mg, 0.003mmol) and N-PMP-α-arylimide ester 1t (0.3mmol), and pass the system through the vacuum line , replace with nitrogen 3 times, add 1 mL of trifluoroethanol solvent, put it into the autoclave, after 6 times of hydrogen replacement, make the initial hydrogen pressure 30bar, stir and react at 50°C for 24 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 98% and the enantiomeric excess was 95%. 2t: Colorless liquid, ¹ H NMR (400MHz, Chloroform-d) δ7.66-7.60 (m, 6H), 7.50-7.46 (m, 2H), 7.42-7.37 (m, 1H), 6.80 (d, J ＝8.8Hz,2H),6.63(d,J＝8.8Hz,2H),5.13(s,1H),3.79(s,3H),3.75(s,3H); ¹³ C NMR(101MHz,Chloroform-d) δ172.6,152.6,141.2,140.6,140.2,136.8,128.8,127.8,127.6,127.5,127.1,114.9,114.8,61.4,55.7,52.8.

Example 86

Preparation of 2u(Ar=PMP, R=3,4-diF-Ph, X=O, R'=CH ₃ )

In a 10mL Schlenck tube, add phosphine ligand L7 (0.003mmol), nickel acetate tetrahydrate (0.75mg, 0.003mmol) and N-PMP-α-arylimide ester 1u (0.3mmol), and pass the system through the vacuum line , replace with nitrogen 3 times, add 1 mL of trifluoroethanol solvent, put it into the autoclave, after 6 times of hydrogen replacement, make the initial hydrogen pressure 30bar, stir and react at 50°C for 24 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 86% and the enantiomeric excess was 95%. 2u: Colorless liquid, ¹ H NMR (400MHz, Chloroform-d) 7.36-7.30 (m, 1H), 7.26-7.22 (m, 1H), 7.16-7.09 (m, 1H), 6.72 (d, J＝9.2 Hz, 2H), 6.48 (d, J = 9.2Hz, 2H), 4.96 (s, 1H), 4.74 (s, 1H), 3.73 (s, 3H), 3.70 (s, 3H); ¹³ C NMR (101MHz ,Chloroform-d)δ171.9,153.0,150.8(dd,J＝250.5Hz,13.1Hz),150.5(dd,J＝250.5Hz,12.1Hz),139.8,135.2(t,J＝3.0Hz),123.5(t , J=5.1Hz), 117.8 (d, J=17.2Hz), 116.5 (d, J=17.2Hz), 115.1, 115.0, 60.9, 55.9, 53.2; ¹⁹ F NMR (376MHz, Chloroform-d) δ-137.04 ,-138.67.

Example 87

Preparation of 2v (Ar=PMP, R=2,5-diF-Ph, X=O, R'=CH ₃ )

In a 10mL Schlenck tube, add phosphine ligand L7 (0.003mmol), nickel acetate tetrahydrate (0.75mg, 0.003mmol) and N-PMP-α-arylimide ester 1v (0.3mmol), and pass the system through the vacuum line , replace with nitrogen 3 times, add 1 mL of trifluoroethanol solvent, put it into the autoclave, after 6 times of hydrogen replacement, make the initial hydrogen pressure 30bar, stir and react at 50°C for 24 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 98% and the enantiomeric excess was 96%. 2v: colorless liquid, ¹ H NMR (400MHz, Chloroform-d) δ7.26-7.17 (m, 1H), 6.87 (t, J = 8.0Hz, 2H), 6.73 (d, J = 8.8Hz, 2H) ,6.67(d,J＝8.8Hz,2H),5.50(s,1H),4.65(s,1H),3.73(s,3H),3.69(s,3H); ¹³ C NMR(101MHz,Chloroform-d )δ171.1,161.2(dd,J＝249.5Hz,8.1Hz),153.0,139.9,129.9(t,J＝10.1Hz),115.4,115.2(t,J＝15.2Hz),114.9,111.8(dd,J＝ 20.2Hz, 7.1Hz), 55.6, 53.0, 52.0 (t, J = 2.0Hz); ¹⁹ F NMR (376MHz, Chloroform-d) δ-115.44.

Example 88

Preparation of 2w (Ar=PMP, R=2F-6MeO-Ph, X=O, R'=CH ₃ )

In a 10mL Schlenck tube, add phosphine ligand L7 (0.003mmol), nickel acetate tetrahydrate (0.75mg, 0.003mmol) and N-PMP-α-arylimide ester 1w (0.3mmol), and the system passes through the vacuum line , replace with nitrogen 3 times, add 1 mL of trifluoroethanol solvent, put it into the autoclave, after 6 times of hydrogen replacement, make the initial hydrogen pressure 30bar, stir and react at 50°C for 24 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 99% and the enantiomeric excess was 96%. 2w: colorless liquid, ¹ H NMR (400MHz, Chloroform-d) δ7.21-7.15(m,1H),6.74-6.64(m,6H),5.56(s,1H),4.70(s,1H), 3.85 (s, 3H), 3.69 (s, 6H); ¹³ C NMR (101MHz, Chloroform-d) δ 172.3 (d, J = 1.0Hz), 161.4 (d, J = 246.4Hz), 158.4 (d, J＝8.1Hz),152.8,140.7,129.7(d,J＝11.1Hz),115.5,115.1(d,J＝16.2Hz),114.7,108.4(d,J＝23.2Hz),106.9(d,J＝ 3.0Hz), 56.2, 55.6, 52.6, 52.2 (d, J = 3.0Hz); ¹⁹ F NMR (376MHz, Chloroform-d) δ-116.99.

Example 89

Preparation of 2x(Ar=PMP, R=2,4-diMe-Ph, X=O, R'=CH ₃ )

In a 10mL Schlenck tube, add phosphine ligand L7 (0.003mmol), nickel acetate tetrahydrate (0.75mg, 0.003mmol) and N-PMP-α-arylimide ester 1x (0.3mmol), and pass the system through the vacuum line , replace with nitrogen 3 times, add 1 mL of trifluoroethanol solvent, put it into the autoclave, after 6 times of hydrogen replacement, make the initial hydrogen pressure 30bar, stir and react at 50°C for 24 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 97% and the enantiomeric excess was 98%. 2x: Colorless liquid, ¹ H NMR (400MHz, Chloroform-d) δ7.25 (d, J＝8.0Hz, 1H), 7.01-6.97 (m, 2H), 6.71 (d, J＝9.2Hz, 2H) ,6.50(d,J＝9.2Hz,2H),5.18(s,1H),4.49(s,1H),3.68(s,3H),3.678(s,3H),2.47(s,3H),2.28( s, 3H); ¹³ C NMR (101MHz, Chloroform-d) δ 173.2, 152.6, 140.6, 137.9, 136.4, 133.2, 131.8, 127.3, 126.5, 114.9, 114.6, 58.1, 55.7, 52.6, 21.1, 19.4.

Example 90

Preparation of 2y (Ar=PMP, R=3,4-diMeo, X=O, R'=CH ₃ )

In a 10mL Schlenck tube, add phosphine ligand L7 (0.003mmol), nickel acetate tetrahydrate (0.75mg, 0.003mmol) and N-PMP-α-arylimide ester 1y (0.3mmol), and the system is passed through the vacuum line , replace with nitrogen 3 times, add 1 mL of trifluoroethanol solvent, put it into the autoclave, after 6 times of hydrogen replacement, make the initial hydrogen pressure 30bar, stir and react at 50°C for 24 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 99% and the enantiomeric excess was 96%. 2y: colorless liquid, ¹ H NMR (400MHz, Chloroform-d) δ7.04-7.00 (m, 2H), 6.83 (d, J = 8.0Hz, 1H), 6.73 (d, J = 8.8Hz, 2H) ,6.54(d,J＝8.8Hz,2H),4.94(s,1H),4.62(s,1H),3.86(s,3H),3.85(s,3H),3.71(s,3H),3.69( s, 3H); ¹³ C NMR (101MHz, Chloroform-d) δ 172.8, 152.6, 149.3, 149.0, 140.3, 130.2, 119.7, 114.84, 114.82, 111.3, 110.1, 61.4, 55.9, 55.89, 55.7, 52.7.

Example 91

Preparation of 2z (Ar=PMP, R=3,4OCH ₂ -Ph, X=O, R'=CH ₃ )

In a 10mL Schlenck tube, add phosphine ligand L7 (0.003mmol), nickel acetate tetrahydrate (0.75mg, 0.003mmol) and N-PMP-α-arylimide ester 1z (0.3mmol), and pass the system through a vacuum line , replace with nitrogen 3 times, add 1 mL of trifluoroethanol solvent, put it into the autoclave, after 6 times of hydrogen replacement, make the initial hydrogen pressure 30bar, stir and react at 50°C for 24 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 99% and the enantiomeric excess was 94%. 2z: Colorless liquid, ¹ H NMR (400MHz, Chloroform-d) δ6.96-6.94 (m, 2H), 6.76 (d, J = 8.4Hz, 1H), 6.71 (d, J = 8.8Hz, 2H) ,6.51(d,J＝8.8Hz,2H),5.92-5.91(m,2H),4.91(s,1H),4.65(s,1H),3.71(s,3H),3.69(s,3H); ¹³ CNMR(101MHz,Chloroform-d)δ172.5,152.5,148.1,147.6,140.1,131.7,120.9,114.9,114.8,108.5,107.6,101.2,61.2,55.7,52.8.

Example 92

Preparation of 2aa (Ar=PMP, R=2-naphthyl, X=O, R'=CH ₃ )

In a 10mL Schlenck tube, add phosphine ligand L7 (0.003mmol), nickel acetate tetrahydrate (0.75mg, 0.003mmol) and N-PMP-α-arylimide ester 1aa (0.3mmol), and pass the system through a vacuum line , replace with nitrogen 3 times, add 1 mL of trifluoroethanol solvent, put it into the autoclave, after 6 times of hydrogen replacement, make the initial hydrogen pressure 30bar, stir and react at 50°C for 24 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 98% and the enantiomeric excess was 92%. 2aa: Colorless liquid, ¹ H NMR (400MHz, Chloroform-d) δ7.95 (s, 1H), 7.83-7.79 (m, 3H), 7.59 (d, J = 8.4Hz, 1H), 7.48-7.44 ( m,2H),6.70(d,J＝8.0Hz,2H),6.56(d,J＝8.0Hz,2H),5.17(s,1H),4.80(s,1H),3.70(s,3H), 3.66 (s, 3H); ¹³ C NMR (101MHz, Chloroform-d) δ172.5,152.6,140.2,135.4,133.4,133.3,128.8,128.1,127.7,126.5,126.4,126.3,125.0,114.9,114.86,6 1.8,55.7 ,52.8.

Example 93

Preparation of 2ab (Ar=PMP, R=1-naphthyl, X=O, R'=CH ₃ )

In a 10mL Schlenck tube, add phosphine ligand L7 (0.003mmol), nickel acetate tetrahydrate (0.75mg, 0.003mmol) and N-PMP-α-arylimide ester 1ab (0.3mmol), and pass the system through a vacuum line , replace with nitrogen 3 times, add 1 mL of trifluoroethanol solvent, put it into the autoclave, after 6 times of hydrogen replacement, make the initial hydrogen pressure 30bar, stir and react at 50°C for 24 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 81% and the enantiomeric excess was 95%. 2ab: Colorless liquid, ¹ H NMR (400MHz, Chloroform-d) δ8.28 (d, J＝9.2Hz, 1H), 7.88 (d, J＝8.0Hz, 1H), 7.81 (d, J＝9.2Hz ,1H),7.63-7.49(m,3H),7.44-7.40(m,1H),6.69(d,J＝8.8Hz,2H),6.53(d,J＝8.8Hz,2H),5.76(s, 1H),4.61(s,1H),3.67(s,3H),3.66(s,3H); ¹³ C NMR(101MHz,Chloroform-d)δ173.0,152.6,140.5,134.2,133.6,131.4,129.1,129.0, 126.7,126.0,125.6,125.1,123.4,114.9,114.6,58.4,55.7,52.8

Example 94

Preparation of 2ac (Ar=PMP, R=Ph, X=O, R’=Et)

In a 10mL Schlenck tube, add phosphine ligand L7 (0.003mmol), nickel acetate tetrahydrate (0.75mg, 0.003mmol) and N-PMP-α-arylimide ester 1ac (0.3mmol), and pass the system through a vacuum line , replace with nitrogen 3 times, add 1 mL of trifluoroethanol solvent, put it into the autoclave, after 6 times of hydrogen replacement, make the initial hydrogen pressure 30bar, stir and react at 50°C for 24 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 99% and the enantiomeric excess was 96%. 2ac: Colorless liquid, ¹ H NMR (400MHz, Chloroform-d) 7.48 (d, J＝6.8Hz, 2H), 7.34-7.25 (m, 3H), 6.70 (d, J＝8.8Hz, 2H), 6.52 (d,J＝8.8Hz,2H),5.00(s,1H),4.67(s,1H),4.23-4.06(m,2H),3.66(s,3H),1.17(t,J＝7.2Hz, 3H); ¹³ C NMR (101MHz, Chloroform-d) δ172.1,152.5,140.3,138.0,128.8,128.2,127.3,114.9,114.8,61.8,61.7,55.7,14.1

Example 95

Preparation of 2ad (Ar=PMP, R=Ph, X=O, R’=i-Pr)

In a 10mL Schlenck tube, add phosphine ligand L7 (0.003mmol), nickel acetate tetrahydrate (0.75mg, 0.003mmol) and N-PMP-α-arylimide ester 1ad (0.3mmol), and pass the system through a vacuum line , replace with nitrogen 3 times, add 1 mL of trifluoroethanol solvent, put it into the autoclave, after 6 times of hydrogen replacement, make the initial hydrogen pressure 30bar, stir and react at 50°C for 24 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 99% and the enantiomeric excess was 95%. 2ad: Colorless liquid, ¹ H NMR (400MHz, Chloroform-d) δ7.47 (d, J＝7.2Hz, 2H), 7.34-7.24 (m, 3H), 6.70 (d, J＝8.8Hz, 2H) ,6.52(d,J＝8.8Hz,2H),5.06-4.98(m,1H),4.97(d,J＝3.9Hz,1H),4.67(s,1H),3.67(s,3H),1.24( d, J＝6.4Hz, 3H), 1.06 (d, J＝6.0Hz, 3H); ¹³ C NMR (101MHz, Chloroform-d) δ 171.6, 152.5, 140.4, 138.0, 128.7, 128.1, 127.2, 114.9, 114.8, 69.4,61.8,55.7,21.8,21.4.

Example 96

Preparation of 2ae (Ar=PMP, R=Ph, X=O, R’=Bn)

In a 10mL Schlenck tube, add phosphine ligand L7 (0.003mmol), nickel acetate tetrahydrate (0.75mg, 0.003mmol) and N-PMP-α-arylimide ester 1ae (0.3mmol), and pass the system through a vacuum line , replace with nitrogen 3 times, add 1 mL of trifluoroethanol solvent, put it into the autoclave, after 6 times of hydrogen replacement, make the initial hydrogen pressure 30bar, stir and react at 50°C for 24 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 91% and the enantiomeric excess was 92%. 2ae: colorless liquid, ¹ H NMR (400MHz, Chloroform-d) δ7.47 (d, J = 6.0Hz, 2H), 7.34-7.26 (m, 6H), 7.15-7.13 (m, 2H), 6.69 ( d, J＝8.8Hz, 2H), 6.51 (d, J＝8.8Hz, 2H), 5.18-5.06 (m, 3H), 4.67 (s, 1H), 3.66 (s, 3H); ¹³ C NMR (101MHz ,Chloroform-d)δ172.0,152.6,140.2,137.7,135.4,128.9,128.6,128.4,128.3,127.9,127.4,114.9,114.87,67.3,61.8,55.7.

Example 97

Preparation of 2af (Ar=PMP, R=Ph, X=N, R’=i-Pr)

In a 10mL Schlenck tube, add phosphine ligand L7 (0.003mmol), nickel acetate (0.75mg, 0.003mmol) and N-PMP-α-aryliminamide 1af (0.3mmol), and pass the system through a vacuum line with Replace with nitrogen 3 times, add 1 mL of trifluoroethanol solvent, and put it into the autoclave. After 6 times of hydrogen replacement, make the initial hydrogen pressure 30 bar and stir the reaction at 70°C for 24 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 81% and the enantiomeric excess was 95%. 2af: Colorless liquid, ¹ H NMR (400MHz, Chloroform-d) δ7.42-7.30 (m, 5H), 6.77 (d, J = 8.8Hz, 2H), 6.72 (d, J = 8.8Hz, 1H) ,6.58(d,J＝8.8Hz,2H),4.61(s,1H),4.21(s,1H),4.14-4.06(m,1H),3.73(s,3H),1.14(d,J＝6.8 Hz, 3H), 1.06 (d, J = 6.8 Hz, 3H); ¹³ C NMR (101MHz, Chloroform-d) δ 170.4, 153.2, 140.9, 139.1, 129.1, 128.5, 127.4, 115.0, 114.8, 65.2, 55.7, 41.3 ,22.7,22.5.

Example 98

Preparation of 2ag (Ar=PMP, R=Ph, R’=pyrrolidine)

In a 10mL Schlenck tube, add phosphine ligand L7 (0.003mmol), nickel acetate tetrahydrate (0.75mg, 0.003mmol) and N-PMP-α-aryliminamide 1ag (0.3mmol), and pass the system through a vacuum line , replace with nitrogen 3 times, add 1 mL of trifluoroethanol solvent, put it into the autoclave, after 6 times of hydrogen replacement, make the initial hydrogen pressure 30bar, stir and react at 50°C for 24 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 85% and the enantiomeric excess was 91%. 2ag: colorless liquid, ¹ H NMR (400MHz, Chloroform-d) δ7.45 (d, J = 8.0Hz, 2H), 7.31 (t, J = 7.2Hz, 2H), 7.26-7.23 (m, 1H) ,6.69(d,J＝8.8Hz,2H),6.58(d,J＝8.8Hz,2H),5.00(s,1H),3.67(s,3H),3.63-3.51(m,2H),3.43- 3.36(m,1H),3.28-3.23(m,1H),1.93-1.67(m,4H); ¹³ C NMR(101MHz,Chloroform-d)δ169.4,152.2,140.8,138.4,128.8,128.0,128.0,115.2 ,114.8,60.9,55.7,46.4,46.3,26.0,23.9.

Example 99

Preparation of 2ah (Ar=Ph, R=Ph, X=O, R'=CH ₃ )

In a 10mL Schlenck tube, add phosphine ligand L7 (0.003mmol), nickel acetate tetrahydrate (0.75mg, 0.003mmol) and N-phenyl-α-arylimide ester 1ah (0.3mmol), and pass the system through the vacuum line , replace with nitrogen 3 times, add 1 mL of trifluoroethanol solvent, put it into the autoclave, after 6 times of hydrogen replacement, make the initial hydrogen pressure 30bar, stir and react at 50°C for 24 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 93% and the enantiomeric excess was 95%. 2ah: Colorless liquid, ¹ H NMR (400MHz, Chloroform-d) ¹ H NMR (400MHz, Chloroform-d) δ7.51-7.49(m,2H),7.38-7.31(m,3H),7.14-7.11( m,2H),6.71(t,J＝7.6Hz,1H),6.57(d,J＝7.6Hz,2H),5.09(s,1H),4.92(s,1H),3.77(s,3H); ¹³ C NMR (101 MHz, Chloroform-d) δ 172.6, 146.2, 137.8, 129.5, 129.1, 128.5, 127.5, 118.4, 113.6, 61.0, 53.0.

Example 100

Preparation of 2ai (Ar=p-ClC ₆ H ₄ (p-chlorophenyl),, R=Ph, X=O, R'=CH ₃ )

In a 10mL Schlenck tube, add phosphine ligand L7 (0.003mmol), nickel acetate tetrahydrate (0.75mg, 0.003mmol) and Np-chlorophenyl-α-arylimide ester 1ai (0.3mmol), and the system is passed through the vacuum line , replace with nitrogen 3 times, add 1 mL of trifluoroethanol solvent, put it into the autoclave, after 6 times of hydrogen replacement, make the initial hydrogen pressure 30bar, stir and react at 50°C for 24 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 99% and the enantiomeric excess was 96%. 2ah: Colorless liquid, ¹ H NMR (400MHz, Chloroform-d) δ7.50 (d, J＝6.8Hz, 2H), 7.43-7.32 (m, 3H), 7.09 (d, J＝8.8Hz, 2H) ,6.50(d,J＝8.8Hz,2H),5.06(s,1H),3.76(s,3H); ¹³ C NMR(101MHz,Chloroform-d)δ172.0,144.4,137.1,129.1,129.0,128.5,127.2 ,122.8,114.5,60.7,52.9.

Example 101

Preparation of 2aj (Ar=p-BrC ₆ H ₄ (p-bromophenyl), R=Ph, X=O, R'=CH ₃ )

In a 10mL Schlenck tube, add phosphine ligand L7 (0.003mmol), nickel acetate tetrahydrate (0.75mg, 0.003mmol) and Np-bromophenyl-α-arylimide ester 1aj (0.3mmol), and the system is passed through the vacuum line , replace with nitrogen 3 times, add 1 mL of trifluoroethanol solvent, put it into the autoclave, after 6 times of hydrogen replacement, make the initial hydrogen pressure 30bar, stir and react at 50°C for 24 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 99% and the enantiomeric excess was 94%. 2ah: Colorless liquid, ¹ H NMR (400MHz, Chloroform-d) δ7.49 (d, J＝6.8Hz, 2H), 7.42-7.31 (m, 3H), 7.22 (d, J＝8.8Hz, 2H) ,6.45(d,J=8.8Hz,2H),5.05(s,1H),3.76(s,3H); ¹³ C NMR(101MHz,Chloroform-d)δ172.0,144.8,137.1,132.0,129.0,128.5,127.2 ,115.0,109.9,60.6,52.9.

Example 102

Preparation of 2ak (Ar=2,6-diMeC ₆ H ₃ (2,6-dimethylphenyl), R=CH ₃ , X=O, R'=CH ₃ )

In a 10mL Schlenck tube, add phosphine ligand L7 (0.003mmol), nickel acetate tetrahydrate (0.75mg, 0.003mmol) and N-2,6-dimethylphenyl-α-methyl imide ester 1ak (0.3mmol), The system passed through the vacuum line, replaced with nitrogen three times, added 1 mL of trifluoroethanol solvent, and put it into an autoclave. After six hydrogen replacements, the initial hydrogen pressure was set to 30 bar, and the reaction was stirred at 50°C for 24 hours. Cool, release the gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion rate by NMR, and obtain the product by column chromatography. The yield was 94% and the enantiomeric excess was 98%. 2ah: colorless liquid, ¹ HNMR (400MHz, Chloroform-d) δ6.96 (d, J = 7.6Hz, 2H), 6.79 (t, J = 7.6Hz, 1H), 3.98 (q, J = 6.8Hz, 1H), 3.66 (s, 3H), 2.29 (s, 6H), 1.37 (d, J = 6.8Hz, 3H); ¹³ C NMR (101MHz, Chloroform-d) δ 176.0, 144.0, 129.0, 128.9, 121.9, 55.1 ,52.0,19.7,18.7.

Specific embodiments of the present invention have been described above. It should be understood that the present invention is not limited to the specific embodiments described above. Those skilled in the art can make various changes or modifications within the scope of the claims, which does not affect the essence of the present invention. The embodiments of the present application and the features in the embodiments can be combined with each other arbitrarily without conflict.

Claims (44)

1. A method for preparing chiral glycine derivatives by asymmetric nickel catalytic hydrogenation, characterized in that the asymmetric nickel hydrogenation substrate is N -aryl-α-imidate ester amide, and the method comprises the following steps: in a solvent, under a certain hydrogen pressure and temperature, catalyzed by a nickel chiral catalyst, hydrogenating the N -aryl-α-imidate ester amide represented by general formula (1) to a chiral glycine derivative represented by general formula (2): In the general formulas (1) and (2), Ar represents naphthalene; R represents any one selected from phenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 2-bromophenyl, 3-bromophenyl, 4-bromophenyl, 2-iodophenyl, 3-iodophenyl, 4-iodophenyl, 1-naphthyl, 2-naphthyl, 3,4-dimethoxyphenyl, 3,4-dimethylphenyl, 3,4-dichlorophenyl, 3,4-piperazinylphenyl, 2,4-dimethylphenyl, or an alkyl group having 1 to 6 carbon atoms; X represents oxygen or nitrogen; R ^' represents an alkyl group having 1 to 6 carbon atoms, or represents any one selected from phenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 2-bromophenyl, 3-bromophenyl, 4-bromophenyl, 2-iodophenyl, 3-iodophenyl, 4-iodophenyl, 1-naphthyl, 2-naphthyl, 3,4-dimethoxyphenyl, 3,4-dimethylphenyl, 3,4-dichlorophenyl, 3,4-piperazinylphenyl, and 2,4-dimethylphenyl; The nickel chiral catalyst is formed by complexing a nickel salt with different anions and a chiral ligand; The chiral ligand refers to any one ligand selected from L1 to L17, and the structural formulas of the ligands L1 to L17 are as follows: In _{L1-L6, Ar' is selected from C6H5, 4-CH3OC6H4, 4-CF3C6H4 or} ^3,5 _{- di - tBu - 4 - MeOC6H2} . 2. The method for preparing chiral glycine derivatives by asymmetric nickel-catalyzed hydrogenation according to claim 1, characterized in that the nickel salt with different anions refers to a nickel salt whose anion is any one of chloride, bromide, acetate, trifluoroacetate, trifluoromethanesulfonate and perchlorate, containing water or not. 3. The method for preparing chiral glycine derivatives by asymmetric nickel-catalyzed hydrogenation according to claim 1, characterized in that the solvent is a mixture of one or more non-polar solvents and polar solvents. 4. The method for preparing chiral glycine derivatives by asymmetric nickel-catalyzed hydrogenation according to claim 3, characterized in that the non-polar solvent is at least one of toluene, ether, and tetrahydrofuran; and the polar solvent is at least one of dichloromethane, 1,2-dichloroethane, DMF, acetone, and acetonitrile. 5. The method for preparing chiral glycine derivatives by asymmetric nickel-catalyzed hydrogenation according to claim 1, characterized in that in the general formulas (1) and (2), R and R' each represent any one selected from methyl, ethyl, isopropyl, n-butyl, and cyclohexyl. 6. The method for preparing chiral glycine derivatives by asymmetric nickel-catalyzed hydrogenation according to claim 1, characterized in that the hydrogen pressure is 5 to 80 bar; and the temperature is 0°C to 100°C. 7. The method for preparing chiral glycine derivatives by asymmetric nickel-catalyzed hydrogenation according to claim 1, characterized in that the molar ratio of the nickel chiral catalyst to the N-aryl-α-imidate ester amide represented by the general formula (1) is 1:20 to 10000; and the hydrogenation time is 6 to 72 hours. 8. A method for preparing chiral glycine derivatives by asymmetric nickel-catalyzed hydrogenation, characterized in that the method comprises: adding 0.004 mmol of phosphine ligand L7, 0.004 mmol of nickel acetate tetrahydrate and 8 mmol of N-PMP-α-aryl imine ester 1a to a 10 mL Schlenck tube, replacing the system with nitrogen for 3 times, adding 9 mL of trifluoroethanol solvent, loading into an autoclave, and after 6 hydrogen replacements, making the initial hydrogen pressure 50 bar, stirring and reacting at 70° C. for 48 hours; cooling, carefully releasing the gas, opening the autoclave, taking out the vial, draining the solvent, detecting the conversion rate by NMR, and obtaining the product by column chromatography; the phosphine ligand L7 is ; The N-PMP-α-aryl imine ester 1a is ; where Ar = PMP, R = Ph, X = O, R ^' = CH ₃ . 9. A method for preparing chiral glycine derivatives by asymmetric nickel-catalyzed hydrogenation, characterized in that the method comprises: adding 0.003 mmol of phosphine ligand L7, 0.003 mmol of nickel acetate tetrahydrate and 0.3 mmol of N-PMP-α-aryl imine ester 1b to a 10 mL Schlenck tube, replacing the system with nitrogen for 3 times, adding 1 mL of trifluoroethanol solvent, loading into an autoclave, and after 6 hydrogen replacements, making the initial hydrogen pressure 30 bar, stirring and reacting at 50° C. for 24 hours; cooling, carefully releasing the gas, opening the autoclave, taking out the vial, draining the solvent, detecting the conversion rate by NMR, and obtaining the product by column chromatography; the phosphine ligand L7 is ; The N-PMP-α-aryl imine ester 1b is ; where Ar = PMP, R = 2-F-Ph, X= O, R ^' = CH ₃ . 10. A method for preparing chiral glycine derivatives by asymmetric nickel-catalyzed hydrogenation, characterized in that the method comprises: adding 0.003 mmol of phosphine ligand L7, 0.003 mmol of nickel acetate and 0.3 mmol of N-PMP-α-aryl imine ester 1c to a 10 mL Schlenck tube, replacing the system with nitrogen for 3 times, adding 1 mL of trifluoroethanol solvent, loading into an autoclave, and after 6 hydrogen replacements, making the initial hydrogen pressure 30 bar, stirring and reacting at 50° C. for 24 hours; cooling, carefully releasing the gas, opening the autoclave, taking out the vial, draining the solvent, detecting the conversion rate by NMR, and obtaining the product by column chromatography; the phosphine ligand L7 is ; The N-PMP-α-aryl imine ester 1c is ; Wherein, Ar = PMP, R = 2-Cl-Ph, X = O, R ^' = CH ₃ . 11. A method for preparing chiral glycine derivatives by asymmetric nickel-catalyzed hydrogenation, characterized in that the method comprises: adding 0.003 mmol of phosphine ligand L7, 0.003 mmol of nickel acetate tetrahydrate and 0.3 mmol of N-PMP-α-aryl imine ester 1d into a 10 mL Schlenck tube, replacing the system with nitrogen for 3 times, adding 1 mL of trifluoroethanol solvent, loading into an autoclave, and after 6 hydrogen replacements, making the initial hydrogen pressure 30 bar, stirring and reacting at 50° C. for 24 hours; cooling, carefully releasing the gas, opening the autoclave, taking out the vial, draining the solvent, detecting the conversion rate by NMR, and obtaining the product by column chromatography; the phosphine ligand L7 is ; The N-PMP-α-aryl imine ester 1d is ; Among them, Ar = PMP, R = 2-Br-Ph, X = O, R ^' = CH ₃ . 12. A method for preparing chiral glycine derivatives by asymmetric nickel-catalyzed hydrogenation, characterized in that the method comprises: adding 0.003 mmol of phosphine ligand L7, 0.003 mmol of nickel acetate tetrahydrate and 0.3 mmol of N-PMP-α-aryl imine ester 1e to a 10 mL Schlenck tube, replacing the system with nitrogen for 3 times, adding 1 mL of trifluoroethanol solvent, loading into an autoclave, and after 6 hydrogen replacements, making the initial hydrogen pressure 30 bar, stirring and reacting at 50° C. for 24 hours; cooling, carefully releasing the gas, opening the autoclave, taking out the vial, draining the solvent, detecting the conversion rate by NMR, and obtaining the product by column chromatography; the phosphine ligand L7 is ; The N-PMP-α-aryl imine ester 1e is ; Among them, Ar = PMP, R = 2-CF ₃ -Ph, X = O, R ^' = CH ₃ . 13. A method for preparing chiral glycine derivatives by asymmetric nickel-catalyzed hydrogenation, characterized in that the method comprises: adding 0.003 mmol of phosphine ligand L7, 0.003 mmol of nickel acetate tetrahydrate and 0.3 mmol of N-PMP-α-aryl imine ester 1f to a 10 mL Schlenck tube, replacing the system with nitrogen for 3 times, adding 1 mL of trifluoroethanol solvent, loading into an autoclave, and after 6 hydrogen replacements, making the initial hydrogen pressure 30 bar, stirring and reacting at 50° C. for 24 hours; cooling, carefully releasing the gas, opening the autoclave, taking out the vial, draining the solvent, detecting the conversion rate by NMR, and obtaining the product by column chromatography; the phosphine ligand L7 is ; The N-PMP-α-aryl imine ester 1f is ; Where, Ar = PMP, R = 2-Me-Ph, X = O, R ^' = CH ₃ . 14. A method for preparing chiral glycine derivatives by asymmetric nickel-catalyzed hydrogenation, characterized in that the method comprises: adding 0.003 mmol of phosphine ligand L7, 0.003 mmol of nickel acetate tetrahydrate and 1 g 0.3 mmol of N-PMP-α-aryl imine ester to a 10 mL Schlenck tube, replacing the system with nitrogen for 3 times, adding 1 mL of trifluoroethanol solvent, loading into an autoclave, and after 6 hydrogen replacements, making the initial hydrogen pressure 30 bar, stirring and reacting at 50° C. for 24 hours; cooling, carefully releasing the gas, opening the autoclave, taking out the vial, draining the solvent, detecting the conversion rate by NMR, and obtaining the product by column chromatography; the phosphine ligand L7 is ; The N-PMP-α-aryl imine ester 1g is ; Wherein, Ar = PMP, R = 2-MeOPh, X = O, R ^' = CH ₃ . 15. A method for preparing chiral glycine derivatives by asymmetric nickel-catalyzed hydrogenation, characterized in that the method comprises: adding 0.003 mmol of phosphine ligand L7, 0.003 mmol of nickel acetate tetrahydrate and 0.3 mmol of N-PMP-α-aryl imine ester 1h into a 10 mL Schlenck tube, replacing the system with nitrogen for 3 times, adding 1 mL of trifluoroethanol solvent, loading into an autoclave, and after 6 hydrogen replacements, making the initial hydrogen pressure 30 bar, stirring and reacting at 50° C. for 24 hours; cooling, carefully releasing the gas, opening the autoclave, taking out the vial, draining the solvent, detecting the conversion rate by NMR, and obtaining the product by column chromatography; the phosphine ligand L7 is ; The N-PMP-α-aryl imine ester 1h is ; where Ar = PMP, R = 3-F-Ph, X = O, R ^' = CH ₃ . 16. A method for preparing chiral glycine derivatives by asymmetric nickel-catalyzed hydrogenation, characterized in that the method comprises: adding 0.003 mmol of phosphine ligand L7, 0.003 mmol of nickel acetate tetrahydrate and 0.3 mmol of N-PMP-α-aryl imine ester 1i into a 10 mL Schlenck tube, replacing the system with nitrogen for 3 times, adding 1 mL of trifluoroethanol solvent, loading into an autoclave, and after 6 hydrogen replacements, making the initial hydrogen pressure 30 bar, stirring and reacting at 50° C. for 24 hours; cooling, carefully releasing the gas, opening the autoclave, taking out the vial, draining the solvent, detecting the conversion rate by NMR, and obtaining the product by column chromatography; the phosphine ligand L7 is ; The N-PMP-α-aryl imine ester 1i is ; Wherein, Ar = PMP, R = 3-Cl-Ph, X = O, R ^' = CH ₃ . 17. A method for preparing chiral glycine derivatives by asymmetric nickel-catalyzed hydrogenation, characterized in that the method comprises: adding 0.003 mmol of phosphine ligand L7, 0.003 mmol of nickel acetate tetrahydrate and 0.3 mmol of N-PMP-α-aryl imine ester 1j to a 10 mL Schlenck tube, replacing the system with nitrogen for 3 times, adding 1 mL of trifluoroethanol solvent, loading into an autoclave, and after 6 hydrogen replacements, making the initial hydrogen pressure 30 bar, stirring and reacting at 50° C. for 24 hours; cooling, carefully releasing the gas, opening the autoclave, taking out the vial, draining the solvent, detecting the conversion rate by NMR, and obtaining the product by column chromatography; the phosphine ligand L7 is ; The N-PMP-α-aryl imine ester 1j is ; Among them, Ar = PMP, R = 3-Br-Ph, X = O, R ^' = CH ₃ . 18. A method for preparing chiral glycine derivatives by asymmetric nickel-catalyzed hydrogenation, characterized in that the method comprises: adding 0.003 mmol of phosphine ligand L7, 0.003 mmol of nickel acetate tetrahydrate and 0.3 mmol of N-PMP-α-aryl imine ester 1k to a 10 mL Schlenck tube, replacing the system with nitrogen for 3 times, adding 1 mL of trifluoroethanol solvent, loading into an autoclave, and after 6 hydrogen replacements, making the initial hydrogen pressure 30 bar, stirring and reacting at 70°C for 24 hours; cooling, carefully releasing the gas, opening the autoclave, taking out the vial, draining the solvent, detecting the conversion rate by NMR, and obtaining the product by column chromatography; the phosphine ligand L7 is ; The N-PMP-α-aryl imine ester 1k is ; where Ar = PMP, R = 3-NO ₂ -Ph, X = O, R ^' = CH ₃ . 19. A method for preparing chiral glycine derivatives by asymmetric nickel-catalyzed hydrogenation, characterized in that the method comprises: adding 0.003 mmol of phosphine ligand L7, 0.003 mmol of nickel acetate tetrahydrate and 0.3 mmol of N-PMP-α-aryl imine ester 11 into a 10 mL Schlenck tube, replacing the system with nitrogen for 3 times, adding 1 mL of trifluoroethanol solvent, loading into an autoclave, and after 6 hydrogen replacements, making the initial hydrogen pressure 30 bar, stirring and reacting at 50° C. for 24 hours; cooling, carefully releasing the gas, opening the autoclave, taking out the vial, draining the solvent, detecting the conversion rate by NMR, and obtaining the product by column chromatography; the phosphine ligand L7 is The N-PMP-α-aryl imine ester 11 is ; Where, Ar = PMP, R = 3-Me-Ph, X = O, R ^' = CH ₃ . 20. A method for preparing chiral glycine derivatives by asymmetric nickel-catalyzed hydrogenation, characterized in that the method comprises: adding 0.003 mmol of phosphine ligand L7, 0.003 mmol of nickel acetate tetrahydrate and 0.3 mmol of N-PMP-α-aryl imine ester 1m into a 10 mL Schlenck tube, replacing the system with nitrogen for 3 times, adding 1 mL of trifluoroethanol solvent, loading into an autoclave, and after 6 hydrogen replacements, making the initial hydrogen pressure 30 bar, stirring and reacting at 50° C. for 24 hours; cooling, carefully releasing the gas, opening the autoclave, taking out the vial, draining the solvent, detecting the conversion rate by NMR, and obtaining the product by column chromatography; the phosphine ligand L7 is ; The N-PMP-α-aryl imine ester 1m is ; Wherein, Ar = PMP, R = 3-MeO-Ph, X = O, R ^' = CH ₃ . 21. A method for preparing chiral glycine derivatives by asymmetric nickel-catalyzed hydrogenation, characterized in that the method comprises: adding 0.003 mmol of phosphine ligand L7, 0.003 mmol of nickel acetate tetrahydrate and 0.3 mmol of N-PMP-α-aryl imine ester 1n into a 10 mL Schlenck tube, replacing the system with nitrogen for 3 times, adding 1 mL of trifluoroethanol solvent, loading into an autoclave, and after 6 hydrogen replacements, making the initial hydrogen pressure 30 bar, stirring and reacting at 50° C. for 24 hours; cooling, carefully releasing the gas, opening the autoclave, taking out the vial, draining the solvent, detecting the conversion rate by NMR, and obtaining the product by column chromatography; the phosphine ligand L7 is ; The N-PMP-α-aryl imine ester 1n is ; Wherein, Ar = PMP, R = 4-F-Ph, X = O, R ^' = CH ₃ . 22. A method for preparing chiral glycine derivatives by asymmetric nickel-catalyzed hydrogenation, characterized in that the method comprises: adding 0.003 mmol of phosphine ligand L7, 0.003 mmol of nickel acetate tetrahydrate and 0.3 mmol of N-PMP-α-aryl imine ester 1o into a 10 mL Schlenck tube, replacing the system with nitrogen for 3 times, adding 1 mL of trifluoroethanol solvent, loading into an autoclave, and after 6 hydrogen replacements, making the initial hydrogen pressure 30 bar, stirring and reacting at 50° C. for 24 hours; cooling, carefully releasing the gas, opening the autoclave, taking out the vial, draining the solvent, detecting the conversion rate by NMR, and obtaining the product by column chromatography; the phosphine ligand L7 is ; The N-PMP-α-aryl imine ester 1o is ; Wherein, Ar = PMP, R = 4-Cl-Ph, X = O, R ^' = CH ₃ . 23. A method for preparing chiral glycine derivatives by asymmetric nickel-catalyzed hydrogenation, characterized in that the method comprises: adding 0.003 mmol of phosphine ligand L7, 0.003 mmol of nickel acetate tetrahydrate and 0.3 mmol of N-PMP-α-aryl imine ester 1p to a 10 mL Schlenck tube, replacing the system with nitrogen for 3 times, adding 1 mL of trifluoroethanol solvent, loading into an autoclave, and after 6 hydrogen replacements, making the initial hydrogen pressure 30 bar, stirring and reacting at 50° C. for 24 hours; cooling, carefully releasing the gas, opening the autoclave, taking out the vial, draining the solvent, detecting the conversion rate by NMR, and obtaining the product by column chromatography; the phosphine ligand L7 is ; The N-PMP-α-aryl imine ester 1p is ; Among them, Ar = PMP, R = 4-Br-Ph, X = O, R ^' = CH ₃ . 24. A method for preparing chiral glycine derivatives by asymmetric nickel-catalyzed hydrogenation, characterized in that the method comprises: adding 0.003 mmol of phosphine ligand L7, 0.003 mmol of nickel acetate tetrahydrate and 0.3 mmol of N-PMP-α-aryl imine ester 1q into a 10 mL Schlenck tube, replacing the system with nitrogen for 3 times, adding 1 mL of trifluoroethanol solvent, loading into an autoclave, and after 6 hydrogen replacements, making the initial hydrogen pressure 30 bar, stirring and reacting at 50° C. for 24 hours; cooling, carefully releasing the gas, opening the autoclave, taking out the vial, draining the solvent, detecting the conversion rate by NMR, and obtaining the product by column chromatography; the phosphine ligand L7 is ; The N-PMP-α-aryl imine ester 1q is ; Where, Ar = PMP, R = 4-CF ₃ -Ph, X = O, R ^' = CH ₃ . 25. A method for preparing chiral glycine derivatives by asymmetric nickel-catalyzed hydrogenation, characterized in that the method comprises: adding 0.003 mmol of phosphine ligand L7, 0.003 mmol of nickel acetate tetrahydrate and 0.3 mmol of N-PMP-α-aryl imine ester 1r into a 10 mL Schlenck tube, replacing the system with nitrogen for 3 times, adding 1 mL of trifluoroethanol solvent, loading into an autoclave, and after 6 hydrogen replacements, making the initial hydrogen pressure 30 bar, stirring and reacting at 50° C. for 24 hours; cooling, carefully releasing the gas, opening the autoclave, taking out the vial, draining the solvent, detecting the conversion rate by NMR, and obtaining the product by column chromatography; the phosphine ligand L7 is ; The N-PMP-α-aryl imine ester 1r is ; Where, Ar = PMP, R = 4-Me-Ph, X = O, R ^' = CH ₃ . 26. A method for preparing chiral glycine derivatives by asymmetric nickel-catalyzed hydrogenation, characterized in that the method comprises: adding 0.003 mmol of phosphine ligand L7, 0.003 mmol of nickel acetate tetrahydrate and 0.3 mmol of N-PMP-α-aryl imine ester 1s into a 10 mL Schlenck tube, replacing the system with nitrogen for 3 times, adding 1 mL of trifluoroethanol solvent, loading into an autoclave, and after 6 hydrogen replacements, making the initial hydrogen pressure 30 bar, stirring and reacting at 50° C. for 24 hours; cooling, carefully releasing the gas, opening the autoclave, taking out the vial, draining the solvent, detecting the conversion rate by NMR, and obtaining the product by column chromatography; the phosphine ligand L7 is ; The N-PMP-α-aryl imine ester 1s is ; Wherein, Ar = PMP, R = 4-MeO-Ph, X = O, R ^' = CH ₃ . 27. A method for preparing chiral glycine derivatives by asymmetric nickel-catalyzed hydrogenation, characterized in that the method comprises: adding 0.003 mmol of phosphine ligand L7, 0.003 mmol of nickel acetate tetrahydrate and 0.3 mmol of N-PMP-α-aryl imine ester 1t into a 10 mL Schlenck tube, replacing the system with nitrogen for 3 times, adding 1 mL of trifluoroethanol solvent, loading into an autoclave, and after 6 hydrogen replacements, making the initial hydrogen pressure 30 bar, stirring and reacting at 50° C. for 24 hours; cooling, carefully releasing the gas, opening the autoclave, taking out the vial, draining the solvent, detecting the conversion rate by NMR, and obtaining the product by column chromatography; the phosphine ligand L7 is ; The N-PMP-α-aryl imine ester 1t is ; where Ar = PMP, R = 4-Ph-Ph, X = O, R ^' = CH ₃ . 28. A method for preparing chiral glycine derivatives by asymmetric nickel-catalyzed hydrogenation, characterized in that the method comprises: adding 0.003 mmol of phosphine ligand L7, 0.003 mmol of nickel acetate tetrahydrate and 0.3 mmol of N-PMP-α-aryl imine ester 1u into a 10 mL Schlenck tube, replacing the system with nitrogen for 3 times, adding 1 mL of trifluoroethanol solvent, loading into an autoclave, and after 6 hydrogen replacements, making the initial hydrogen pressure 30 bar, stirring and reacting at 50° C. for 24 hours; cooling, carefully releasing the gas, opening the autoclave, taking out the vial, draining the solvent, detecting the conversion rate by NMR, and obtaining the product by column chromatography; the phosphine ligand L7 is ; The N-PMP-α-aryl imine ester 1u is ;where Ar = PMP, R = 3,4-diF-Ph, X = O,R ^' = CH ₃ . 29. A method for preparing chiral glycine derivatives by asymmetric nickel-catalyzed hydrogenation, characterized in that the method comprises: adding 0.003 mmol of phosphine ligand L7, 0.003 mmol of nickel acetate tetrahydrate and 0.3 mmol of N-PMP-α-aryl imine ester 1v into a 10 mL Schlenck tube, replacing the system with nitrogen for 3 times, adding 1 mL of trifluoroethanol solvent, loading into an autoclave, and after 6 hydrogen replacements, making the initial hydrogen pressure 30 bar, stirring and reacting at 50°C for 24 hours; cooling, carefully releasing the gas, opening the autoclave, taking out the vial, draining the solvent, detecting the conversion rate by NMR, and obtaining the product by column chromatography; the phosphine ligand L7 is ; The N-PMP-α-aryl imine ester 1v is ;where Ar = PMP, R = 2,5-diF-Ph, X = O,R ^' = CH ₃ . 30. A method for preparing chiral glycine derivatives by asymmetric nickel-catalyzed hydrogenation, characterized in that the method comprises: adding 0.003 mmol of phosphine ligand L7, 0.003 mmol of nickel acetate tetrahydrate and 0.3 mmol of N-PMP-α-aryl imine ester 1w into a 10 mL Schlenck tube, replacing the system with nitrogen for 3 times, adding 1 mL of trifluoroethanol solvent, loading into an autoclave, and after 6 hydrogen replacements, making the initial hydrogen pressure 30 bar, stirring and reacting at 50° C. for 24 hours; cooling, carefully releasing the gas, opening the autoclave, taking out the vial, draining the solvent, detecting the conversion rate by NMR, and obtaining the product by column chromatography; the phosphine ligand L7 is ; The N-PMP-α-aryl imine ester 1w is ; Wherein, Ar = PMP, R = 2F-6MeO-Ph, X = O, R ^' = CH ₃ . 31. A method for preparing chiral glycine derivatives by asymmetric nickel-catalyzed hydrogenation, characterized in that the method comprises: adding 0.003 mmol of phosphine ligand L7, 0.003 mmol of nickel acetate tetrahydrate and 1x 0.3 mmol of N-PMP-α-aryl imine ester to a 10 mL Schlenck tube, replacing the system with nitrogen for 3 times, adding 1 mL of trifluoroethanol solvent, loading into an autoclave, and after 6 hydrogen replacements, making the initial hydrogen pressure 30 bar, stirring and reacting at 50° C. for 24 hours; cooling, carefully releasing the gas, opening the autoclave, taking out the vial, draining the solvent, detecting the conversion rate by NMR, and obtaining the product by column chromatography; the phosphine ligand L7 is ; The N-PMP-α-aryl imine ester 1x is ; Wherein, Ar = PMP, R = 2,4-diMe-Ph, X = O, R ^' = CH ₃ . 32. A method for preparing chiral glycine derivatives by asymmetric nickel-catalyzed hydrogenation, characterized in that the method comprises: adding 0.003 mmol of phosphine ligand L7, 0.003 mmol of nickel acetate tetrahydrate and 0.3 mmol of N-PMP-α-aryl imine ester 1y to a 10 mL Schlenck tube, replacing the system with nitrogen for 3 times, adding 1 mL of trifluoroethanol solvent, loading into an autoclave, and after 6 hydrogen replacements, making the initial hydrogen pressure 30 bar, stirring and reacting at 50° C. for 24 hours; cooling, carefully releasing the gas, opening the autoclave, taking out the vial, draining the solvent, detecting the conversion rate by NMR, and obtaining the product by column chromatography; the phosphine ligand L7 is The N-PMP-α-aryl imine ester 1y is ; where Ar = PMP, R = 3,4 -diMeo, X = O, R ^' = CH ₃ . 33. A method for preparing chiral glycine derivatives by asymmetric nickel-catalyzed hydrogenation, characterized in that the method comprises: adding 0.003 mmol of phosphine ligand L7, 0.003 mmol of nickel acetate tetrahydrate and 0.3 mmol of N-PMP-α-aryl imine ester 1z to a 10 mL Schlenck tube, replacing the system with nitrogen for 3 times, adding 1 mL of trifluoroethanol solvent, loading into an autoclave, and after 6 hydrogen replacements, making the initial hydrogen pressure 30 bar, stirring and reacting at 50° C. for 24 hours; cooling, carefully releasing the gas, opening the autoclave, taking out the vial, draining the solvent, detecting the conversion rate by NMR, and obtaining the product by column chromatography; the phosphine ligand L7 is The N-PMP-α-aryl imine ester 1z is ; wherein Ar = PMP, R = 3,4OCH ₂ -Ph, X = O, R ^' = CH ₃ . 34. A method for preparing chiral glycine derivatives by asymmetric nickel-catalyzed hydrogenation, characterized in that the method comprises: adding 0.003 mmol of phosphine ligand L7, 0.003 mmol of nickel acetate tetrahydrate and 0.3 mmol of N-PMP-α-aryl imine ester 1aa into a 10 mL Schlenck tube, replacing the system with nitrogen for 3 times, adding 1 mL of trifluoroethanol solvent, loading into an autoclave, and after 6 hydrogen replacements, making the initial hydrogen pressure 30 bar, stirring and reacting at 50° C. for 24 hours; cooling, carefully releasing the gas, opening the autoclave, taking out the vial, draining the solvent, detecting the conversion rate by NMR, and obtaining the product by column chromatography; the phosphine ligand L7 is ; The N-PMP-α-aryl imine ester 1aa is ;where Ar = PMP, R = 2-naphthyl, X = O,R ^' = CH ₃ . 35. A method for preparing chiral glycine derivatives by asymmetric nickel-catalyzed hydrogenation, characterized in that the method comprises: adding 0.003 mmol of phosphine ligand L7, 0.003 mmol of nickel acetate tetrahydrate and 0.3 mmol of N-PMP-α-aryl imine ester 1ab to a 10 mL Schlenck tube, replacing the system with nitrogen for 3 times, adding 1 mL of trifluoroethanol solvent, loading into an autoclave, and after 6 hydrogen replacements, making the initial hydrogen pressure 30 bar, stirring and reacting at 50° C. for 24 hours; cooling, carefully releasing the gas, opening the autoclave, taking out the vial, draining the solvent, detecting the conversion rate by NMR, and obtaining the product by column chromatography; the phosphine ligand L7 is ; The N-PMP-α-aryl imine ester 1ab is ;where Ar = PMP, R = 1-naphthyl, X = O, R ^' = CH ₃ . 36. A method for preparing chiral glycine derivatives by asymmetric nickel-catalyzed hydrogenation, characterized in that the method comprises: adding 0.003 mmol of phosphine ligand L7, 0.003 mmol of nickel acetate tetrahydrate and 0.3 mmol of N-PMP-α-aryl imine ester 1ac to a 10 mL Schlenck tube, replacing the system with nitrogen for 3 times, adding 1 mL of trifluoroethanol solvent, loading into an autoclave, and after 6 hydrogen replacements, making the initial hydrogen pressure 30 bar, stirring and reacting at 50° C. for 24 hours; cooling, carefully releasing the gas, opening the autoclave, taking out the vial, draining the solvent, detecting the conversion rate by NMR, and obtaining the product by column chromatography; the phosphine ligand L7 is ; The N-PMP-α-aryl imine ester 1ac is ; where Ar = PMP, R = Ph, X= O, R ^' = Et. 37. A method for preparing chiral glycine derivatives by asymmetric nickel-catalyzed hydrogenation, characterized in that the method comprises: adding 0.003 mmol of phosphine ligand L7, 0.003 mmol of nickel acetate tetrahydrate and 0.3 mmol of N-PMP-α-aryl imine ester 1ad into a 10 mL Schlenck tube, replacing the system with nitrogen for 3 times, adding 1 mL of trifluoroethanol solvent, loading into an autoclave, and after 6 hydrogen replacements, making the initial hydrogen pressure 30 bar, stirring and reacting at 50° C. for 24 hours; cooling, carefully releasing the gas, opening the autoclave, taking out the vial, draining the solvent, detecting the conversion rate by NMR, and obtaining the product by column chromatography; the phosphine ligand L7 is ; The N-PMP-α-aryl imine ester 1ad is ; Among them, Ar = PMP, R = Ph, X= O, R ^' = i -Pr. 38. A method for preparing chiral glycine derivatives by asymmetric nickel-catalyzed hydrogenation, characterized in that the method comprises: adding 0.003 mmol of phosphine ligand L7, 0.003 mmol of nickel acetate tetrahydrate and 0.3 mmol of N-PMP-α-aryl imine ester 1ae to a 10 mL Schlenck tube, replacing the system with nitrogen for 3 times, adding 1 mL of trifluoroethanol solvent, loading into an autoclave, and after 6 hydrogen replacements, making the initial hydrogen pressure 30 bar, stirring and reacting at 50° C. for 24 hours; cooling, carefully releasing the gas, opening the autoclave, taking out the vial, draining the solvent, detecting the conversion rate by NMR, and obtaining the product by column chromatography; the phosphine ligand L7 is ; The N-PMP-α-aryl imine ester 1ae is ; where Ar = PMP, R = Ph, X= O, R ^' = Bn. 39. A method for preparing chiral glycine derivatives by asymmetric nickel-catalyzed hydrogenation, characterized in that the method comprises: adding 0.003 mmol of phosphine ligand L7, 0.003 mmol of nickel acetate tetrahydrate and 0.3 mmol of N-PMP-α-aryl imine amide 1af into a 10 mL Schlenck tube, replacing the system with nitrogen for 3 times, adding 1 mL of trifluoroethanol solvent, loading into an autoclave, and after 6 hydrogen replacements, making the initial hydrogen pressure 30 bar, stirring and reacting at 70°C for 24 hours; cooling, carefully releasing the gas, opening the autoclave, taking out the vial, draining the solvent, detecting the conversion rate by NMR, and obtaining the product by column chromatography; the phosphine ligand L7 is ; The N-PMP-α-aryl imine ester 1af is ; Among them, Ar = PMP, R = Ph, X = N, R ^' = i -Pr. 40. A method for preparing chiral glycine derivatives by asymmetric nickel-catalyzed hydrogenation, characterized in that the method comprises: adding 0.003 mmol of phosphine ligand L7, 0.003 mmol of nickel acetate tetrahydrate and 0.3 mmol of N-PMP-α-aryl imine amide 1ag into a 10 mL Schlenck tube, replacing the system with nitrogen for 3 times, adding 1 mL of trifluoroethanol solvent, loading into an autoclave, and after 6 hydrogen replacements, making the initial hydrogen pressure 30 bar, stirring and reacting at 50°C for 24 hours; cooling, carefully releasing the gas, opening the autoclave, taking out the vial, draining the solvent, detecting the conversion rate by NMR, and obtaining the product by column chromatography; the phosphine ligand L7 is ; The N-PMP-α-aryl imine ester 1ag is ; where Ar = PMP, R = Ph, R ^' = pyrrolidine. 41. A method for preparing chiral glycine derivatives by asymmetric nickel-catalyzed hydrogenation, characterized in that the method comprises: adding 0.003 mmol of phosphine ligand L7, 0.003 mmol of nickel acetate tetrahydrate and 0.3 mmol of N-phenyl-α-aryl imine ester 1ah into a 10 mL Schlenck tube, replacing the system with nitrogen for 3 times, adding 1 mL of trifluoroethanol solvent, loading into an autoclave, and after 6 hydrogen replacements, making the initial hydrogen pressure 30 bar, stirring and reacting at 50° C. for 24 hours; cooling, carefully releasing the gas, opening the autoclave, taking out the vial, draining the solvent, detecting the conversion rate by NMR, and obtaining the product by column chromatography; the phosphine ligand L7 is ; The N-phenyl-α-aryl imine ester 1ah is ; where Ar = PMP, R = Ph, X = O, R ^' = CH ₃ . 42. A method for preparing chiral glycine derivatives by asymmetric nickel-catalyzed hydrogenation, characterized in that the method comprises: adding 0.003 mmol of phosphine ligand L7, 0.003 mmol of nickel acetate tetrahydrate and 0.3 mmol of Np-chlorophenyl-α-aryl imide ester 1ai into a 10 mL Schlenck tube, replacing the system with nitrogen for 3 times, adding 1 mL of trifluoroethanol solvent, loading into an autoclave, and after 6 hydrogen replacements, making the initial hydrogen pressure 30 bar, stirring and reacting at 50° C. for 24 hours; cooling, carefully releasing the gas, opening the autoclave, taking out the vial, draining the solvent, detecting the conversion rate by NMR, and obtaining the product by column chromatography; the phosphine ligand L7 is ; The Np-chlorophenyl-α-aryl imine ester 1ai is ; where Ar = PMP, R = Ph, X = O, R ^' = CH ₃ . 43. A method for preparing chiral glycine derivatives by asymmetric nickel-catalyzed hydrogenation, characterized in that the method comprises: adding 0.003 mmol of phosphine ligand L7, 0.003 mmol of nickel acetate tetrahydrate and 0.3 mmol of Np-bromophenyl-α-aryl imine ester 1aj to a 10 mL Schlenck tube, replacing the system with nitrogen for 3 times, adding 1 mL of trifluoroethanol solvent, loading into an autoclave, and after 6 hydrogen replacements, making the initial hydrogen pressure 30 bar, stirring and reacting at 50°C for 24 hours; cooling, carefully releasing the gas, opening the autoclave, taking out the vial, draining the solvent, detecting the conversion rate by NMR, and obtaining the product by column chromatography; the phosphine ligand L7 is ; The Np-bromophenyl-α-aryl imine ester 1aj is ; where Ar = PMP, R = Ph, X = O, R ^' = CH ₃ . 44. A method for preparing chiral glycine derivatives by asymmetric nickel-catalyzed hydrogenation, characterized in that the method comprises: adding 0.003 mmol of phosphine ligand L7, 0.003 mmol of nickel acetate tetrahydrate and 0.3 mmol of N-2,6-dimethylphenyl-α-methyliminoester 1ak into a 10 mL Schlenck tube, replacing the system with nitrogen for 3 times, adding 1 mL of trifluoroethanol solvent, loading into an autoclave, and after 6 hydrogen replacements, making the initial hydrogen pressure 30 bar, stirring and reacting at 50° C. for 24 hours; cooling, carefully releasing the gas, opening the autoclave, taking out the vial, draining the solvent, detecting the conversion rate by NMR, and obtaining the product by column chromatography; the phosphine ligand L7 is ; The N-2,6-dimethylphenyl-α-methylimino ester 1ak is ; Among them, Ar = PMP, R = CH ₃ , X = O, R ^' = CH ₃ .