CN109942506B - Method for preparing chiral amine by asymmetric nickel catalytic hydrogenation of N-sulfimide - Google Patents

Abstract

The invention discloses a method for preparing chiral amine by catalyzing and hydrogenating N-sulfimide by asymmetric nickel; the method comprises the following steps: hydrogenating N-sulfonimide represented by a general formula (1) into chiral amine compound represented by a general formula (2) under catalysis of a chiral catalyst of nickel in a solvent under certain hydrogen pressure and temperature; the structural formulae of the general formulae (1) and (2) are as follows:

Description

Method for preparing chiral amine by asymmetric nickel catalytic hydrogenation of N-sulfimide

Technical Field

The invention relates to the technical field of chemical industry, in particular to a method for preparing chiral amine by catalyzing and hydrogenating N-sulfimide by asymmetric nickel.

Background

Chiral amine compounds are a useful backbone 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, fendiline, rivastigmine, cinacalcet, rasagiline, inhibitors of IDH1 and CLK1, and some steroids, etc. This is a widely used class of basic structures (Chiral Amine Synthesis: Methods, Developments and Applications (Ed.: T.C. Nugent), Wiley-VCH, Weinheim, 2010).

The literature search of the prior art shows that the chiral compound can be obtained by a general method of extraction, resolution, biology or synthesis from chiral raw materials, and has great limitations and uneconomical performance.

Meanwhile, different attempts have been made to chemically asymmetric synthesis methods. At present, the catalyst is obtained by catalyzing asymmetric hydrogenation of enamine or imine by noble metal, and the industrial application of the catalyst is greatly hindered by expensive metal salt and heavy metal ions which are difficult to remove in the catalytic system. Although the newly found inexpensive transition metal catalyst solves the above problems, the catalytic activity is required to be improved. For example, in 2017, the tension mourn group reported that nickel catalyzed beta-enamine esters to chiral beta-amino esters achieved a maximum number of conversions of 570 and an enantioselectivity of 99% (chem. sci.2017,8,6419). In 2018, professor Chirik reported that cobalt catalyzed hydrogenation of α -enamine esters to α -amino ester compounds resulted in a maximum conversion of 1250 and an enantioselectivity of 98% (science 2018,360,888).

In summary, chiral amine compounds are a class of chiral substances with a wide range of applications. The development of a green and efficient synthesis method becomes the focus of current research, and no relevant report is provided so far for synthesizing the compounds with high yield and high enantioselectivity by using an efficient nickel-catalyzed asymmetric imine hydrogenation method.

The Chinese patent application with the application number of 201010577301.2 discloses a method for asymmetric catalytic hydrogenation reaction of ketone derived N-alkyl imine through the search of the prior patent documents. The method of the invention uses chiral catalyst formed by chiral diamine ligand and transition metal to carry out catalytic hydrogenation reaction on N-alkyl imine derived from ketone, and chiral amine product is obtained with high yield and high enantioselectivity. However, the invention patent uses metal complexes of ruthenium, rhodium and iridium as catalysts, is expensive, easily causes heavy metal residues, has large pollution, and greatly limits the application of the catalyst in industry.

Disclosure of Invention

Aiming at the defects in the prior art, the invention provides a method for preparing chiral amine by catalyzing and hydrogenating N-sulfimide by asymmetric nickel; the method for the first time uses the method for the asymmetric catalytic hydrogenation of imine by using cheap transition metal, prepares the chiral amine compound in a green, safe and high-efficiency manner, and has the advantages of simple operation, high yield, good enantioselectivity and the like.

The purpose of the invention is realized by the following technical scheme:

the invention provides a method for preparing chiral amine by catalyzing and hydrogenating N-sulfimide through asymmetric nickel, which comprises the following steps: hydrogenating N-sulfimide represented by a general formula (1) into chiral amine compound represented by a general formula (2) under the catalysis of a chiral catalyst of nickel in a solvent under certain hydrogen pressure and temperature;

wherein R is¹An aryl group having or not having a substituent, an alkyl group having 1 to 8 carbon atoms having or not having a substituent, or an unsaturated substituent having 2 to 8 carbon atoms having or not having a substituent;

R²an aryl group having or not having a substituent, an alkyl group having 1 to 8 carbon atoms having or not having a substituent, or an unsaturated substituent having 2 to 8 carbon atoms having or not having a substituent;

R³the aryl group may be an aryl group having or not having a substituent, an alkyl group having 1 to 8 carbon atoms having or not having a substituent, an aryloxy group having 4 to 8 carbon atoms having or not having a substituent, or an arylamine group having 4 to 8 carbon atoms having or not having a substituent.

In the above general formulae (1) and (2), R is¹、R²And R³Are separate groups; or said R¹、R²And R³Two or three of which are connected to form a ring.

Preferably, the chiral catalyst of nickel is formed by complexing nickel salts with different anions and chiral ligands.

Preferably, the nickel salt having different anions refers to a nickel salt in which the anion is any one of chloride, bromide, acetate, trifluoroacetate, trifluoromethanesulfonate, sulfate and perchlorate.

Preferably, the chiral ligand refers to any one ligand selected from L1-L17, and the structural formulas of the ligands L1-L17 are shown as follows:

in L1-L6, Ar is selected from C₆H₅、4-CH₃OC₆H₄、4-CF₃C₆H₄Or 3,5-di-tBu-4-MeOC₆H₂，n＝1-10。

Preferably, the chiral ligand is L1-L8, L16 or L17. More preferably, L1d, L2d, L3d, L4d, L5d, L6d, L7, L8.

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

Preferably, the nonpolar solvent is at least one of toluene, diethyl ether and tetrahydrofuran.

Preferably, the polar solvent is at least one of dichloromethane, 1, 2-dichloroethane, DMF, acetone, acetonitrile.

Preferably, the protic solvent is at least one of methanol, ethanol, isopropanol 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 said general formulae (1) and (2), R¹、R²、R³Each represents a group selected from methyl, ethyl, isopropyl, n-butyl, cyclohexyl, phenyl and 2-methylbenzeneA phenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 2-methoxyphenyl group, a 3-methoxyphenyl group, a 4-methoxyphenyl group, a 2-fluorophenyl group, a 3-fluorophenyl group, a 4-fluorophenyl group, a 2-chlorophenyl group, a 3-chlorophenyl group, a 4-chlorophenyl group, a 2-bromophenyl group, a 3-bromophenyl group, a 4-bromophenyl group, a 2-iodophenyl group, a 3-iodophenyl group, a 4-iodophenyl group, a 1-naphthyl group, a 2-naphthyl group, a 3, 4-dimethoxyphenyl group, a 3, 4-dimethylphenyl group, a 3, 4-dichlorophenyl group, a 3, 4-piperonyl phenyl group, a 2, 4-dimethylphenyl group, a 2, 4-dimethoxyphenyl 2-furyl group, a five-membered cyclic group, Any one of six-membered cyclic groups;

or in the general formulae (1) and (2), the R¹、R²And R³Can be respectively connected to form a ring shape.

Preferably, the hydrogen pressure is 1 to 80 bar.

Preferably, the molar ratio of the chiral catalyst of nickel to the Z-type N-sulfimide represented by the general formula (1) is 1: 20-100000.

Preferably, the temperature is-78 ℃ to 80 ℃.

Preferably, the hydrogenation time is 1 to 72 hours.

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

the invention uses the method of cheap transition metal asymmetric catalytic hydrogenation imine to efficiently prepare the chiral amine compound for the first time, the reaction method has mild conditions and simple and convenient operation, and can realize good reaction yield and reaction efficiency and has better application effect.

Detailed Description

The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that it would be obvious to those skilled in the art that various changes and modifications can be made without departing from the spirit of the invention. All falling within the scope of the present invention.

The method for preparing chiral amine by catalyzing and hydrogenating N-sulfimide by asymmetric nickel can be represented by the following reaction formula:

in the above reaction formula, the general formula (1) represents N-sulfonimide, and the general formula (2) represents a chiral amine compound.

In the general formulae (1) and (2), R¹Or R²Each represents: an aryl group with or without a substituent, an alkyl group with or without a substituent and having 1 to 8 carbon atoms, or an unsaturated substituent such as an alkenyl group with or without a substituent and having 1 to 8 carbon atoms, or an alkynyl group; wherein the aryl group with or without substituent can be substituted or polysubstituted aryl group such as methyl, methoxy, chlorine, bromine, fluorine or trifluoromethyl, naphthalene and heterocyclic aryl group; the alkyl group having 1 to 8 carbon atoms may be a methyl group, an ethyl group, an isopropyl group, an n-butyl group, a tert-butyl group or a cyclohexyl group.

R³A hetero atom substituent such as an aryl group having or not having a substituent, an alkyl group having 1 to 8 carbon atoms having or not having a substituent, a phenol group having 1 to 8 carbon atoms having or not having a substituent, or an arylamine group; examples of the substituent on the aryl group include a methyl group, a methoxy group, a chlorine group, a bromine group, a fluorine group, a trifluoromethyl group, and other polysubstituent groups.

In the above reaction formula, L × Ni · X represents a chiral catalyst of nickel, that is, an ionic compound of a complex of nickel and a chiral ligand and an anion. Wherein L represents a chiral ligand, and is any one ligand selected from L1 to L17. X represents any one of chloride, bromide, acetate, trifluoroacetate, trifluoromethanesulfonate, sulfate and perchlorate.

In the method for preparing chiral amine by asymmetric nickel catalytic hydrogenation of N-sulfonimide, the hydrogen atmosphere pressure of the hydrogen atmosphere is 1-80 bar, and more preferably 1-50 bar, from the viewpoints of reaction yield and reaction efficiency.

In the method for preparing chiral amine by asymmetric nickel catalytic hydrogenation of N-sulfimide, the molar ratio of the chiral catalyst of nickel to the N-sulfimide represented by the general formula (1) is 1: 20-10, 0000, preferably 1: 50-10000; more preferably 1:50 to 500.

The method for preparing chiral amine by asymmetric nickel catalytic hydrogenation of N-sulfimide of the present invention has a reaction temperature of-78 ℃ to 120 ℃, preferably-40 ℃ to 100 ℃, more preferably 0 ℃ to 80 ℃, and still more preferably 0 ℃ to 60 ℃ from the viewpoint of reaction yield and reaction efficiency; the reaction time is 1 to 72 hours, preferably 5 to 60 hours, more preferably 5 to 48 hours, still more preferably 5 to 36 hours, and particularly preferably 10 to 24 hours.

The invention takes N-sulfimide represented by the general formula (1) as a substrate (org.Lett.2005, 7, 179-182; org.Lett.2008, 10, 2071-2074), and carries out asymmetric catalytic hydrogenation by a chiral catalyst of nickel, thereby obtaining the chiral amine compound represented by the general formula (2). The method has the advantages of mild reaction conditions, simple and convenient operation, good reaction yield and reaction efficiency, and good application effect.

In the following examples, according to R^1-3Different substituents are 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 denote various Z-type N-sulfonimides of formula (1), and 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, 2a, 2Z, 2a, 2Z, 2a, 2ak represents various chiral amine compounds represented by the general formula (2).

It is to be understood that, by the reaction method of the present invention, 2a is produced by asymmetric hydrogenation of 1a, 2b is produced by asymmetric hydrogenation of 1b, 2c is produced by asymmetric hydrogenation of 1c, 2d is produced by asymmetric hydrogenation of 1d, 2e is produced by asymmetric hydrogenation of 1e, 2f is produced by asymmetric hydrogenation of 1f, 2g is produced by asymmetric hydrogenation of 1g, 2h is produced by asymmetric hydrogenation of 1h, 2i is produced by asymmetric hydrogenation of 1i, 2J is produced by asymmetric hydrogenation of 1J, 2k is produced by asymmetric hydrogenation of 1k, 2l is produced by asymmetric hydrogenation of 1l, 2m is produced by asymmetric hydrogenation of 1n, 2o is produced by asymmetric hydrogenation of 1o, 2p is produced by asymmetric hydrogenation of 1p, 2q is produced by asymmetric hydrogenation of 1q, 2r is produced by asymmetric hydrogenation of 1r, 2s is produced by asymmetric hydrogenation of 1s, 2t from 1t asymmetric hydrogenation, 2u from 1u asymmetric hydrogenation, 2v from 1v asymmetric hydrogenation, 2w from 1w asymmetric hydrogenation, 2x from 1x asymmetric hydrogenation, 2y from 1y asymmetric hydrogenation, 2z from 1z asymmetric hydrogenation, 2aa from 1aa asymmetric hydrogenation, 2ab from 1ab asymmetric hydrogenation, 2ac from 1ac asymmetric hydrogenation, 2ad from 1ad asymmetric hydrogenation, 2ae from 1ae asymmetric hydrogenation, 2af from 1af asymmetric hydrogenation, 2ag from 1ag asymmetric hydrogenation, 2ah from 1ah asymmetric hydrogenation, 2ai from 1ai asymmetric hydrogenation, 2aj from 1aj asymmetric hydrogenation, 2ak from 1ak asymmetric hydrogenation.

In the following examples, L × Ni · X represents a chiral catalyst of nickel, as described above, and L1 · Ni · Cl represents a chiral catalyst composed of nickel, a chiral ligand L1, and chloride ions, for example.

And in the following examples, Ar is represented by L1a, L2a, L3a, L4a, L5a, L6a as C according to the difference of Ar substituents₆H₅L1-L6; ar is 4-CH represented by L1b, L2b, L3b, L4b, L5b and L6b₃OC₆H₄L1-L6; ar is 4-CF represented by L1c, L2c, L3c, L4c, L5c and L6c₃C₆H₄L1-L6; ar is 3,5-di-tBu-4-MeOC represented by L1d, L2d, L3d, L4d, L5d and L6d₆H₂L1-L6.

Example 1

2a(R¹＝Ph,R²＝CH₃,R³t-Bu) preparation

To a 10mL Schlenck tube, phosphine ligand L1a (0.002mmol), nickel acetate tetrahydrate (0.5mg,0.002mmol) and N-sulfonimide 1a (0.4mmol) were added, the system was passed through a vacuum line, replaced with nitrogen 3 times, 1mL of trifluoroethanol solvent was added,the mixture was placed in an autoclave, and after 6 times of hydrogen substitution, the initial hydrogen pressure was set to 10bar, and the reaction was stirred at 50 ℃ for 24 hours. Cooling, carefully venting, opening the autoclave, removing the vial, draining the solvent, detecting the conversion by NMR, and performing column chromatography to obtain the product. The yield was 87% and the enantiomeric excess was 95%. 2a, white solid is added into the mixture,¹H NMR(400MHz,Chloroform-d)7.39–7.24(m,5H),4.67(dq,J＝8.4,6.8Hz,1H),4.55(s,1H),1.57(d,J＝6.8Hz,3H),1.31(s,9H)；¹³C NMR(101MHz,Chloroform-d)143.8,129.0,127.7,126.1,60.0,54.7,25.9,24.4.

example 2

2a(R¹＝Ph,R²＝CH₃,R³t-Bu) preparation

To a 10mL Schlenck tube, phosphine ligand L1b (0.002mmol), nickel acetate tetrahydrate (0.5mg,0.002mmol) and N-sulfonimide 1a (0.4mmol) were added, the system was passed through a vacuum line, replaced with nitrogen gas 3 times, 1mL of trifluoroethanol solvent was added, the autoclave was charged, after 6 times of hydrogen replacement, the initial hydrogen pressure was made 10bar, and the reaction was stirred at 50 ℃ for 24 hours. Cooling, carefully venting, opening the autoclave, removing the vial, draining the solvent, detecting the conversion by NMR, and performing column chromatography to obtain the product. The yield was 92% and the enantiomeric excess was 94%. 2a, white solid is added into the mixture,¹H NMR(400MHz,Chloroform-d)7.39–7.24(m,5H),4.67(dq,J＝8.4,6.8Hz,1H),4.55(s,1H),1.57(d,J＝6.8Hz,3H),1.31(s,9H)；¹³C NMR(101MHz,Chloroform-d)143.8,129.0,127.7,126.1,60.0,54.7,25.9,24.4.

example 3

2a(R¹＝Ph,R²＝CH₃,R³t-Bu) preparation

To a 10mL Schlenck tube, phosphine ligand L1c (0.002mmol), nickel acetate tetrahydrate (0.5mg,0.002mmol) and N-sulfonimide 1a (0.4mmol) were added, the system was passed through a vacuum line, replaced with nitrogen gas 3 times, 1mL of trifluoroethanol solvent was added, the autoclave was charged, after 6 times of hydrogen replacement, the initial hydrogen pressure was made 10bar, and the reaction was stirred at 50 ℃ for 24 hours. Cooling, carefully venting, opening the autoclave and removing the vialAnd (4) draining the solvent, detecting the conversion rate by NMR, and carrying out column chromatography to obtain the product. The yield was 95% and the enantiomeric excess was 95%. 2a, white solid is added into the mixture,¹H NMR(400MHz,Chloroform-d)7.39–7.24(m,5H),4.67(dq,J＝8.4,6.8Hz,1H),4.55(s,1H),1.57(d,J＝6.8Hz,3H),1.31(s,9H)；¹³C NMR(101MHz,Chloroform-d)143.8,129.0,127.7,126.1,60.0,54.7,25.9,24.4.

example 4

2a(R¹＝Ph,R²＝CH₃,R³t-Bu) preparation

To a 10mL Schlenck tube, phosphine ligand L1d (0.002mmol), nickel acetate tetrahydrate (0.5mg,0.002mmol) and N-sulfonimide 1a (0.4mmol) were added, the system was passed through a vacuum line, replaced with nitrogen gas 3 times, 1mL of trifluoroethanol solvent was added, the autoclave was charged, after 6 times of hydrogen replacement, the initial hydrogen pressure was made 10bar, and the reaction was stirred at 50 ℃ for 24 hours. Cooling, carefully venting, opening the autoclave, removing the vial, draining the solvent, detecting the conversion by NMR, and performing column chromatography to obtain the product. The yield was 97% and the enantiomeric excess was 98%. 2a, white solid is added into the mixture,¹H NMR(400MHz,Chloroform-d)7.39–7.24(m,5H),4.67(dq,J＝8.4,6.8Hz,1H),4.55(s,1H),1.57(d,J＝6.8Hz,3H),1.31(s,9H)；¹³C NMR(101MHz,Chloroform-d)143.8,129.0,127.7,126.1,60.0,54.7,25.9,24.4.

example 5

2a(R¹＝Ph,R²＝CH₃,R³t-Bu) preparation

To a 10mL Schlenck tube, phosphine ligand L2a (0.002mmol), nickel acetate tetrahydrate (0.5mg,0.002mmol) and N-sulfonimide 1a (0.4mmol) were added, the system was passed through a vacuum line, replaced with nitrogen gas 3 times, 1mL of trifluoroethanol solvent was added, the autoclave was charged, after 6 times of hydrogen replacement, the initial hydrogen pressure was made 10bar, and the reaction was stirred at 50 ℃ for 24 hours. Cooling, carefully venting, opening the autoclave, removing the vial, draining the solvent, detecting the conversion by NMR, and performing column chromatography to obtain the product. The yield was 78% and the enantiomeric excess was 85%. 2a, white solid is added into the mixture,¹H NMR(400MHz,Chloroform-d)7.39–7.24(m,5H),4.67(dq,J＝8.4,6.8Hz,1H),4.55(s,1H),1.57(d,J＝6.8Hz,3H),1.31(s,9H)；¹³C NMR(101MHz,Chloroform-d)143.8,129.0,127.7,126.1,60.0,54.7,25.9,24.4.

example 6

2a(R¹＝Ph,R²＝CH₃,R³t-Bu) preparation

To a 10mL Schlenck tube, phosphine ligand L2b (0.002mmol), nickel acetate tetrahydrate (0.5mg,0.002mmol) and N-sulfonimide 1a (0.4mmol) were added, the system was passed through a vacuum line, replaced with nitrogen gas 3 times, 1mL of trifluoroethanol solvent was added, the autoclave was charged, after 6 times of hydrogen replacement, the initial hydrogen pressure was made 10bar, and the reaction was stirred at 50 ℃ for 24 hours. Cooling, carefully venting, opening the autoclave, removing the vial, draining the solvent, detecting the conversion by NMR, and performing column chromatography to obtain the product. The yield was 82% and the enantiomeric excess was 90%. 2a, white solid is added into the mixture,¹H NMR(400MHz,Chloroform-d)7.39–7.24(m,5H),4.67(dq,J＝8.4,6.8Hz,1H),4.55(s,1H),1.57(d,J＝6.8Hz,3H),1.31(s,9H)；¹³C NMR(101MHz,Chloroform-d)143.8,129.0,127.7,126.1,60.0,54.7,25.9,24.4.

example 7

2a(R¹＝Ph,R²＝CH₃,R³t-Bu) preparation

To a 10mL Schlenck tube, phosphine ligand L2c (0.002mmol), nickel acetate tetrahydrate (0.5mg,0.002mmol) and N-sulfonimide 1a (0.4mmol) were added, the system was passed through a vacuum line, replaced with nitrogen gas 3 times, 1mL of trifluoroethanol solvent was added, the autoclave was charged, after 6 times of hydrogen replacement, the initial hydrogen pressure was made 10bar, and the reaction was stirred at 50 ℃ for 24 hours. Cooling, carefully venting, opening the autoclave, removing the vial, draining the solvent, detecting the conversion by NMR, and performing column chromatography to obtain the product. Cooling, carefully venting, opening the autoclave, removing the vial, draining the solvent, detecting the conversion by NMR, and performing column chromatography to obtain the product. The yield was 85% and the enantiomeric excess was 91%. 2a, white solid is added into the mixture,¹H NMR(400MHz,Chloroform-d)7.39–7.24(m,5H),4.67(dq,J＝8.4,6.8Hz,1H),4.55(s,1H),1.57(d,J＝6.8Hz,3H),1.31(s,9H)；¹³C NMR(101MHz,Chloroform-d)143.8,129.0,127.7,126.1,60.0,54.7,25.9,24.4.

example 8

2a(R¹＝Ph,R²＝CH₃,R³t-Bu) preparation

To a 10mL Schlenck tube, phosphine ligand L2d (0.002mmol), nickel acetate tetrahydrate (0.5mg,0.002mmol) and N-sulfonimide 1a (0.4mmol) were added, the system was passed through a vacuum line, replaced with nitrogen gas 3 times, 1mL of trifluoroethanol solvent was added, the autoclave was charged, after 6 times of hydrogen replacement, the initial hydrogen pressure was made 10bar, and the reaction was stirred at 50 ℃ for 24 hours. Cooling, carefully venting, opening the autoclave, removing the vial, draining the solvent, detecting the conversion by NMR, and performing column chromatography to obtain the product. The yield was 93% and the enantiomeric excess was 95%. 2a, white solid is added into the mixture,¹H NMR(400MHz,Chloroform-d)7.39–7.24(m,5H),4.67(dq,J＝8.4,6.8Hz,1H),4.55(s,1H),1.57(d,J＝6.8Hz,3H),1.31(s,9H)；¹³C NMR(101MHz,Chloroform-d)143.8,129.0,127.7,126.1,60.0,54.7,25.9,24.4.

example 9

2a(R¹＝Ph,R²＝CH₃,R³t-Bu) preparation

To a 10mL Schlenck tube, phosphine ligand L3a (0.002mmol), nickel acetate tetrahydrate (0.5mg,0.002mmol) and N-sulfonimide 1a (0.4mmol) were added, the system was passed through a vacuum line, replaced with nitrogen gas 3 times, 1mL of trifluoroethanol solvent was added, the autoclave was charged, after 6 times of hydrogen replacement, the initial hydrogen pressure was made 10bar, and the reaction was stirred at 50 ℃ for 24 hours. Cooling, carefully venting, opening the autoclave, removing the vial, draining the solvent, detecting the conversion by NMR, and performing column chromatography to obtain the product. The yield was 65% with an enantiomeric excess of 74%. 2a, white solid is added into the mixture,¹H NMR(400MHz,Chloroform-d)7.39–7.24(m,5H),4.67(dq,J＝8.4,6.8Hz,1H),4.55(s,1H),1.57(d,J＝6.8Hz,3H),1.31(s,9H)；¹³C NMR(101MHz,Chloroform-d)143.8,129.0,127.7,126.1,60.0,54.7,25.9,24.4.

practice ofExample 10

2a(R¹＝Ph,R²＝CH₃,R³t-Bu) preparation

To a 10mL Schlenck tube, phosphine ligand L3b (0.002mmol), nickel acetate tetrahydrate (0.5mg,0.002mmol) and N-sulfonimide 1a (0.4mmol) were added, the system was passed through a vacuum line, replaced with nitrogen gas 3 times, 1mL of trifluoroethanol solvent was added, the autoclave was charged, after 6 times of hydrogen replacement, the initial hydrogen pressure was made 10bar, and the reaction was stirred at 50 ℃ for 24 hours. Cooling, carefully venting, opening the autoclave, removing the vial, draining the solvent, detecting the conversion by NMR, and performing column chromatography to obtain the product. The yield was 80% and the enantiomeric excess was 84%. 2a, white solid is added into the mixture,¹H NMR(400MHz,Chloroform-d)7.39–7.24(m,5H),4.67(dq,J＝8.4,6.8Hz,1H),4.55(s,1H),1.57(d,J＝6.8Hz,3H),1.31(s,9H)；¹³C NMR(101MHz,Chloroform-d)143.8,129.0,127.7,126.1,60.0,54.7,25.9,24.4.

example 11

2a(R¹＝Ph,R²＝CH₃,R³t-Bu) preparation

To a 10mL Schlenck tube, phosphine ligand L3c (0.002mmol), nickel acetate tetrahydrate (0.5mg,0.002mmol) and N-sulfonimide 1a (0.4mmol) were added, the system was passed through a vacuum line, replaced with nitrogen gas 3 times, 1mL of trifluoroethanol solvent was added, the autoclave was charged, after 6 times of hydrogen replacement, the initial hydrogen pressure was made 10bar, and the reaction was stirred at 50 ℃ for 24 hours. Cooling, carefully venting, opening the autoclave, removing the vial, draining the solvent, detecting the conversion by NMR, and performing column chromatography to obtain the product. The yield was 72% and the enantiomeric excess was 87%. 2a, white solid is added into the mixture,¹H NMR(400MHz,Chloroform-d)7.39–7.24(m,5H),4.67(dq,J＝8.4,6.8Hz,1H),4.55(s,1H),1.57(d,J＝6.8Hz,3H),1.31(s,9H)；¹³C NMR(101MHz,Chloroform-d)143.8,129.0,127.7,126.1,60.0,54.7,25.9,24.4.

example 12

2a(R¹＝Ph,R²＝CH₃,R³t-Bu) preparation

To a 10mL Schlenck tube, phosphine ligand L3d (0.002mmol), nickel acetate tetrahydrate (0.5mg,0.002mmol) and N-sulfonimide 1a (0.4mmol) were added, the system was passed through a vacuum line, replaced with nitrogen gas 3 times, 1mL of trifluoroethanol solvent was added, the autoclave was charged, after 6 times of hydrogen replacement, the initial hydrogen pressure was made 10bar, and the reaction was stirred at 50 ℃ for 24 hours. Cooling, carefully venting, opening the autoclave, removing the vial, draining the solvent, detecting the conversion by NMR, and performing column chromatography to obtain the product. The yield was 91% and the enantiomeric excess was 92%. 2a, white solid is added into the mixture,¹H NMR(400MHz,Chloroform-d)7.39–7.24(m,5H),4.67(dq,J＝8.4,6.8Hz,1H),4.55(s,1H),1.57(d,J＝6.8Hz,3H),1.31(s,9H)；¹³C NMR(101MHz,Chloroform-d)143.8,129.0,127.7,126.1,60.0,54.7,25.9,24.4.

example 13

2a(R¹＝Ph,R²＝CH₃,R³t-Bu) preparation

To a 10mL Schlenck tube, phosphine ligand L4a (0.002mmol), nickel acetate tetrahydrate (0.5mg,0.002mmol) and N-sulfonimide 1a (0.4mmol) were added, the system was passed through a vacuum line, replaced with nitrogen gas 3 times, 1mL of trifluoroethanol solvent was added, the autoclave was charged, after 6 times of hydrogen replacement, the initial hydrogen pressure was made 10bar, and the reaction was stirred at 50 ℃ for 24 hours. Cooling, carefully venting, opening the autoclave, removing the vial, draining the solvent, detecting the conversion by NMR, and performing column chromatography to obtain the product. The yield was 72% and the enantiomeric excess was 81%. 2a, white solid is added into the mixture,¹H NMR(400MHz,Chloroform-d)7.39–7.24(m,5H),4.67(dq,J＝8.4,6.8Hz,1H),4.55(s,1H),1.57(d,J＝6.8Hz,3H),1.31(s,9H)；¹³C NMR(101MHz,Chloroform-d)143.8,129.0,127.7,126.1,60.0,54.7,25.9,24.4.

example 14

2a(R¹＝Ph,R²＝CH₃,R³t-Bu) preparation

To a 10mL Schlenck tube, phosphine ligand L4b (0.002mmol), nickel acetate tetrahydrate (0.5mg,0.002mmol) and N-sulfonimide 1a (0.4mmol) were added and the system passed through a vacuum line with nitrogenThe replacement was carried out 3 times, 1mL of a trifluoroethanol solvent was added, the mixture was charged into an autoclave, and after 6 times of hydrogen replacement, the initial hydrogen pressure was set to 10bar, and the reaction was carried out at 50 ℃ for 24 hours with stirring. Cooling, carefully venting, opening the autoclave, removing the vial, draining the solvent, detecting the conversion by NMR, and performing column chromatography to obtain the product. The yield was 74% and the enantiomeric excess was 86%. 2a, white solid is added into the mixture,¹H NMR(400MHz,Chloroform-d)7.39–7.24(m,5H),4.67(dq,J＝8.4,6.8Hz,1H),4.55(s,1H),1.57(d,J＝6.8Hz,3H),1.31(s,9H)；¹³C NMR(101MHz,Chloroform-d)143.8,129.0,127.7,126.1,60.0,54.7,25.9,24.4.

example 15

2a(R¹＝Ph,R²＝CH₃,R³t-Bu) preparation

To a 10mL Schlenck tube, phosphine ligand L4c (0.002mmol), nickel acetate tetrahydrate (0.5mg,0.002mmol) and N-sulfonimide 1a (0.4mmol) were added, the system was passed through a vacuum line, replaced with nitrogen gas 3 times, 1mL of trifluoroethanol solvent was added, the autoclave was charged, after 6 times of hydrogen replacement, the initial hydrogen pressure was made 10bar, and the reaction was stirred at 50 ℃ for 24 hours. Cooling, carefully venting, opening the autoclave, removing the vial, draining the solvent, detecting the conversion by NMR, and performing column chromatography to obtain the product. The yield was 87% and the enantiomeric excess was 92%. 2a, white solid is added into the mixture,¹H NMR(400MHz,Chloroform-d)7.39–7.24(m,5H),4.67(dq,J＝8.4,6.8Hz,1H),4.55(s,1H),1.57(d,J＝6.8Hz,3H),1.31(s,9H)；¹³C NMR(101MHz,Chloroform-d)143.8,129.0,127.7,126.1,60.0,54.7,25.9,24.4.

example 16

2a(R¹＝Ph,R²＝CH₃,R³t-Bu) preparation

To a 10mL Schlenck tube, phosphine ligand L4d (0.002mmol), nickel acetate tetrahydrate (0.5mg,0.002mmol) and N-sulfonimide 1a (0.4mmol) were added, the system was passed through a vacuum line, replaced with nitrogen gas 3 times, 1mL of trifluoroethanol solvent was added, the autoclave was charged, after 6 times of hydrogen replacement, the initial hydrogen pressure was made 10bar, and the reaction was stirred at 50 ℃ for 24 hours. Cooling, cautionAnd (4) discharging gas, opening the autoclave, taking out a small bottle, pumping out the solvent, detecting the conversion rate by NMR, and carrying out column chromatography to obtain the product. The yield was 93% and the enantiomeric excess was 94%. 2a, white solid is added into the mixture,¹H NMR(400MHz,Chloroform-d)7.39–7.24(m,5H),4.67(dq,J＝8.4,6.8Hz,1H),4.55(s,1H),1.57(d,J＝6.8Hz,3H),1.31(s,9H)；¹³C NMR(101MHz,Chloroform-d)143.8,129.0,127.7,126.1,60.0,54.7,25.9,24.4.

example 17

2a(R¹＝Ph,R²＝CH₃,R³t-Bu) preparation

To a 10mL Schlenck tube, phosphine ligand L5a (0.002mmol), nickel acetate tetrahydrate (0.5mg,0.002mmol) and N-sulfonimide 1a (0.4mmol) were added, the system was passed through a vacuum line, replaced with nitrogen gas 3 times, 1mL of trifluoroethanol solvent was added, the autoclave was charged, after 6 times of hydrogen replacement, the initial hydrogen pressure was made 10bar, and the reaction was stirred at 50 ℃ for 24 hours. Cooling, carefully venting, opening the autoclave, removing the vial, draining the solvent, detecting the conversion by NMR, and performing column chromatography to obtain the product. The yield was 63% and the enantiomeric excess was 72%. 2a, white solid is added into the mixture,¹H NMR(400MHz,Chloroform-d)7.39–7.24(m,5H),4.67(dq,J＝8.4,6.8Hz,1H),4.55(s,1H),1.57(d,J＝6.8Hz,3H),1.31(s,9H)；¹³C NMR(101MHz,Chloroform-d)143.8,129.0,127.7,126.1,60.0,54.7,25.9,24.4.

example 18

2a(R¹＝Ph,R²＝CH₃,R³t-Bu) preparation

To a 10mL Schlenck tube, phosphine ligand L5b (0.002mmol), nickel acetate tetrahydrate (0.5mg,0.002mmol) and N-sulfonimide 1a (0.4mmol) were added, the system was passed through a vacuum line, replaced with nitrogen gas 3 times, 1mL of trifluoroethanol solvent was added, the autoclave was charged, after 6 times of hydrogen replacement, the initial hydrogen pressure was made 10bar, and the reaction was stirred at 50 ℃ for 24 hours. Cooling, carefully venting, opening the autoclave, removing the vial, draining the solvent, detecting the conversion by NMR, and performing column chromatography to obtain the product. The yield was 81% and the enantiomeric excess was 75%. 2a white solid,¹H NMR(400MHz,Chloroform-d)7.39–7.24(m,5H),4.67(dq,J＝8.4,6.8Hz,1H),4.55(s,1H),1.57(d,J＝6.8Hz,3H),1.31(s,9H)；¹³C NMR(101MHz,Chloroform-d)143.8,129.0,127.7,126.1,60.0,54.7,25.9,24.4.

Example 19

2a(R¹＝Ph,R²＝CH₃,R³t-Bu) preparation

To a 10mL Schlenck tube, phosphine ligand L5c (0.002mmol), nickel acetate tetrahydrate (0.5mg,0.002mmol) and N-sulfonimide 1a (0.4mmol) were added, the system was passed through a vacuum line, replaced with nitrogen gas 3 times, 1mL of trifluoroethanol solvent was added, the autoclave was charged, after 6 times of hydrogen replacement, the initial hydrogen pressure was made 10bar, and the reaction was stirred at 50 ℃ for 24 hours. Cooling, carefully venting, opening the autoclave, removing the vial, draining the solvent, detecting the conversion by NMR, and performing column chromatography to obtain the product. The yield was 85% and the enantiomeric excess was 86%. 2a, white solid is added into the mixture,¹H NMR(400MHz,Chloroform-d)7.39–7.24(m,5H),4.67(dq,J＝8.4,6.8Hz,1H),4.55(s,1H),1.57(d,J＝6.8Hz,3H),1.31(s,9H)；¹³C NMR(101MHz,Chloroform-d)143.8,129.0,127.7,126.1,60.0,54.7,25.9,24.4.

example 20

2a(R¹＝Ph,R²＝CH₃,R³t-Bu) preparation

To a 10mL Schlenck tube, phosphine ligand L5d (0.002mmol), nickel acetate tetrahydrate (0.5mg,0.002mmol) and N-sulfonimide 1a (0.4mmol) were added, the system was passed through a vacuum line, replaced with nitrogen gas 3 times, 1mL of trifluoroethanol solvent was added, the autoclave was charged, after 6 times of hydrogen replacement, the initial hydrogen pressure was made 10bar, and the reaction was stirred at 50 ℃ for 24 hours. Cooling, carefully venting, opening the autoclave, removing the vial, draining the solvent, detecting the conversion by NMR, and performing column chromatography to obtain the product. The yield was 95% and the enantiomeric excess was 93%. 2a, white solid is added into the mixture,¹H NMR(400MHz,Chloroform-d)7.39–7.24(m,5H),4.67(dq,J＝8.4,6.8Hz,1H),4.55(s,1H),1.57(d,J＝6.8Hz,3H),1.31(s,9H)；¹³C NMR(101MHz,Chloroform-d)143.8,129.0,127.7,126.1,60.0,54.7,25.9,24.4.

example 21

2a(R¹＝Ph,R²＝CH₃,R³t-Bu) preparation

To a 10mL Schlenck tube, phosphine ligand L6a (0.002mmol), nickel acetate tetrahydrate (0.5mg,0.002mmol) and N-sulfonimide 1a (0.4mmol) were added, the system was passed through a vacuum line, replaced with nitrogen gas 3 times, 1mL of trifluoroethanol solvent was added, the autoclave was charged, after 6 times of hydrogen replacement, the initial hydrogen pressure was made 10bar, and the reaction was stirred at 50 ℃ for 24 hours. Cooling, carefully venting, opening the autoclave, removing the vial, draining the solvent, detecting the conversion by NMR, and performing column chromatography to obtain the product. The yield was 75% and the enantiomeric excess was 76%. 2a, white solid is added into the mixture,¹H NMR(400MHz,Chloroform-d)7.39–7.24(m,5H),4.67(dq,J＝8.4,6.8Hz,1H),4.55(s,1H),1.57(d,J＝6.8Hz,3H),1.31(s,9H)；¹³C NMR(101MHz,Chloroform-d)143.8,129.0,127.7,126.1,60.0,54.7,25.9,24.4.

example 22

2a(R¹＝Ph,R²＝CH₃,R³t-Bu) preparation

To a 10mL Schlenck tube, phosphine ligand L6b (0.002mmol), nickel acetate tetrahydrate (0.5mg,0.002mmol) and N-sulfonimide 1a (0.4mmol) were added, the system was passed through a vacuum line, replaced with nitrogen gas 3 times, 1mL of trifluoroethanol solvent was added, the autoclave was charged, after 6 times of hydrogen replacement, the initial hydrogen pressure was made 10bar, and the reaction was stirred at 50 ℃ for 24 hours. Cooling, carefully venting, opening the autoclave, removing the vial, draining the solvent, detecting the conversion by NMR, and performing column chromatography to obtain the product. The yield was 78% and the enantiomeric excess was 84%. 2a, white solid is added into the mixture,¹H NMR(400MHz,Chloroform-d)7.39–7.24(m,5H),4.67(dq,J＝8.4,6.8Hz,1H),4.55(s,1H),1.57(d,J＝6.8Hz,3H),1.31(s,9H)；¹³C NMR(101MHz,Chloroform-d)143.8,129.0,127.7,126.1,60.0,54.7,25.9,24.4.

example 23

2a(R¹＝Ph,R²＝CH₃,R³t-Bu) preparation

To a 10mL Schlenck tube, phosphine ligand L6c (0.002mmol), nickel acetate tetrahydrate (0.5mg,0.002mmol) and N-sulfonimide 1a (0.4mmol) were added, the system was passed through a vacuum line, replaced with nitrogen gas 3 times, 1mL of trifluoroethanol solvent was added, the autoclave was charged, after 6 times of hydrogen replacement, the initial hydrogen pressure was made 10bar, and the reaction was stirred at 50 ℃ for 24 hours. Cooling, carefully venting, opening the autoclave, removing the vial, draining the solvent, detecting the conversion by NMR, and performing column chromatography to obtain the product. The yield was 88% and the enantiomeric excess was 85%. 2a, white solid is added into the mixture,¹H NMR(400MHz,Chloroform-d)7.39–7.24(m,5H),4.67(dq,J＝8.4,6.8Hz,1H),4.55(s,1H),1.57(d,J＝6.8Hz,3H),1.31(s,9H)；¹³C NMR(101MHz,Chloroform-d)143.8,129.0,127.7,126.1,60.0,54.7,25.9,24.4.

example 24

2a(R¹＝Ph,R²＝CH₃,R³t-Bu) preparation

To a 10mL Schlenck tube, phosphine ligand L6d (0.002mmol), nickel acetate tetrahydrate (0.5mg,0.002mmol) and N-sulfonimide 1a (0.4mmol) were added, the system was passed through a vacuum line, replaced with nitrogen gas 3 times, 1mL of trifluoroethanol solvent was added, the autoclave was charged, after 6 times of hydrogen replacement, the initial hydrogen pressure was made 10bar, and the reaction was stirred at 50 ℃ for 24 hours. Cooling, carefully venting, opening the autoclave, removing the vial, draining the solvent, detecting the conversion by NMR, and performing column chromatography to obtain the product. The yield was 94% and the enantiomeric excess was 96%. 2a, white solid is added into the mixture,¹H NMR(400MHz,Chloroform-d)7.39–7.24(m,5H),4.67(dq,J＝8.4,6.8Hz,1H),4.55(s,1H),1.57(d,J＝6.8Hz,3H),1.31(s,9H)；¹³C NMR(101MHz,Chloroform-d)143.8,129.0,127.7,126.1,60.0,54.7,25.9,24.4.

example 25

2a(R¹＝Ph,R²＝CH₃,R³t-Bu) preparation

To a 10mL Schlenck tube, phosphine ligand L7(0.002mmol) was added,Nickel acetate tetrahydrate (0.5mg,0.002mmol) and N-sulfonimide 1a (0.4mmol) were passed through a vacuum line, replaced with nitrogen gas 3 times, 1mL of trifluoroethanol solvent was added, the mixture was charged into an autoclave, after 6 times of hydrogen replacement, the initial hydrogen pressure was set to 80bar, and the reaction was stirred at room temperature for 24 hours. Cooling, carefully venting, opening the autoclave, removing the vial, draining the solvent, detecting the conversion by NMR, and performing column chromatography to obtain the product. The yield was 88% and the enantiomeric excess was 93%. 2a, white solid is added into the mixture,¹H NMR(400MHz,Chloroform-d)7.39–7.24(m,5H),4.67(dq,J＝8.4,6.8Hz,1H),4.55(s,1H),1.57(d,J＝6.8Hz,3H),1.31(s,9H)；¹³C NMR(101MHz,Chloroform-d)143.8,129.0,127.7,126.1,60.0,54.7,25.9,24.4.

example 26

2a(R¹＝Ph,R²＝CH₃,R³t-Bu) preparation

To a 10mL Schlenck tube, phosphine ligand L8(0.002mmol), nickel acetate tetrahydrate (0.5mg,0.002mmol) and N-sulfonimide 1a (0.4mmol) were added, the system was passed through a vacuum line, replaced with nitrogen gas 3 times, 1mL of trifluoroethanol solvent was added, the autoclave was charged, after 6 times of replacement with hydrogen gas, the initial hydrogen pressure was made 20bar, and the reaction was stirred at room temperature for 24 hours. Cooling, carefully venting, opening the autoclave, removing the vial, draining the solvent, detecting the conversion by NMR, and performing column chromatography to obtain the product. The yield was 99% and the enantiomeric excess was 99.5%. 2a, white solid is added into the mixture,¹H NMR(400MHz,Chloroform-d)7.39–7.24(m,5H),4.67(dq,J＝8.4,6.8Hz,1H),4.55(s,1H),1.57(d,J＝6.8Hz,3H),1.31(s,9H)；¹³C NMR(101MHz,Chloroform-d)143.8,129.0,127.7,126.1,60.0,54.7,25.9,24.4.

example 27

2a(R¹＝Ph,R²＝CH₃,R³t-Bu) preparation

A10 mL Schlenck tube was charged with phosphine ligand L9(0.002mmol), nickel acetate tetrahydrate (0.5mg,0.002mmol) and N-sulfonimide 1a (0.4mmol), and the system was passed through a vacuum line, replaced with nitrogen gas 3 times, 1mL of trifluoroethanol solvent was added, the autoclave was charged, replaced with hydrogen gas 6 times, and then the mixture was allowed to standThe initial hydrogen pressure was 5bar and the reaction was stirred at room temperature for 24 hours. Cooling, carefully venting, opening the autoclave, removing the vial, draining the solvent, detecting the conversion by NMR, and performing column chromatography to obtain the product. The yield was 92% with an enantiomeric excess of 88%. 2a, white solid is added into the mixture,¹H NMR(400MHz,Chloroform-d)7.39–7.24(m,5H),4.67(dq,J＝8.4,6.8Hz,1H),4.55(s,1H),1.57(d,J＝6.8Hz,3H),1.31(s,9H)；¹³C NMR(101MHz,Chloroform-d)143.8,129.0,127.7,126.1,60.0,54.7,25.9,24.4.

example 28

2a(R¹＝Ph,R²＝CH₃,R³t-Bu) preparation

To a 10mL Schlenck tube, phosphine ligand L10(0.002mmol), nickel acetate tetrahydrate (0.5mg,0.002mmol) and N-sulfonimide 1a (0.4mmol) were added, the system was passed through a vacuum line, replaced with nitrogen gas 3 times, 1mL of trifluoroethanol solvent was added, the autoclave was charged, after 6 times of hydrogen replacement, the initial hydrogen pressure was made 10bar, and the reaction was stirred at 25 ℃ for 48 hours. Cooling, carefully venting, opening the autoclave, removing the vial, draining the solvent, detecting the conversion by NMR, and performing column chromatography to obtain the product. The yield was 85% and the enantiomeric excess was 86%. 2a, white solid is added into the mixture,¹H NMR(400MHz,Chloroform-d)7.39–7.24(m,5H),4.67(dq,J＝8.4,6.8Hz,1H),4.55(s,1H),1.57(d,J＝6.8Hz,3H),1.31(s,9H)；¹³C NMR(101MHz,Chloroform-d)143.8,129.0,127.7,126.1,60.0,54.7,25.9,24.4.

example 29

2a(R¹＝Ph,R²＝CH₃,R³t-Bu) preparation

To a 10mL Schlenck tube, phosphine ligand L11(0.002mmol), nickel acetate tetrahydrate (0.5mg,0.002mmol) and N-sulfonimide 1a (0.4mmol) were added, the system was passed through a vacuum line, replaced with nitrogen gas 3 times, 1mL of trifluoroethanol solvent was added, the autoclave was charged, after 6 times of replacement with hydrogen gas, the initial hydrogen pressure was made 10bar, and the reaction was stirred at room temperature for 36 hours. Cooling, carefully venting, opening the autoclave, removing the vial, draining the solvent, detecting the conversion by NMR, and performing column chromatography to obtain the product. Yield of95% and an enantiomeric excess of 90%. 2a, white solid is added into the mixture,¹H NMR(400MHz,Chloroform-d)7.39–7.24(m,5H),4.67(dq,J＝8.4,6.8Hz,1H),4.55(s,1H),1.57(d,J＝6.8Hz,3H),1.31(s,9H)；¹³C NMR(101MHz,Chloroform-d)143.8,129.0,127.7,126.1,60.0,54.7,25.9,24.4.

example 30

2a(R¹＝Ph,R²＝CH₃,R³t-Bu) preparation

To a 10mL Schlenck tube, phosphine ligand L12(0.002mmol), nickel acetate tetrahydrate (0.5mg,0.002mmol) and N-sulfonimide 1a (0.4mmol) were added, the system was passed through a vacuum line, replaced with nitrogen gas 3 times, 1mL of trifluoroethanol solvent was added, the autoclave was charged, after 6 times of replacement with hydrogen gas, the initial hydrogen pressure was set to 15bar, and the reaction was stirred at room temperature for 10 hours. Cooling, carefully venting, opening the autoclave, removing the vial, draining the solvent, detecting the conversion by NMR, and performing column chromatography to obtain the product. The yield was 81% and the enantiomeric excess was 86%. 2a, white solid is added into the mixture,¹H NMR(400MHz,Chloroform-d)7.39–7.24(m,5H),4.67(dq,J＝8.4,6.8Hz,1H),4.55(s,1H),1.57(d,J＝6.8Hz,3H),1.31(s,9H)；¹³C NMR(101MHz,Chloroform-d)143.8,129.0,127.7,126.1,60.0,54.7,25.9,24.4.

example 31

2a(R¹＝Ph,R²＝CH₃,R³t-Bu) preparation

To a 10mL Schlenck tube, phosphine ligand L13(0.002mmol), nickel acetate tetrahydrate (0.5mg,0.002mmol) and N-sulfonimide 1a (0.4mmol) were added, the system was passed through a vacuum line, replaced with nitrogen gas 3 times, 1mL of trifluoroethanol solvent was added, the autoclave was charged, and after 6 times of hydrogen replacement, the initial hydrogen pressure was set to 35bar, and the reaction was stirred at-78 ℃ for 24 hours. Cooling, carefully venting, opening the autoclave, removing the vial, draining the solvent, detecting the conversion by NMR, and performing column chromatography to obtain the product. The yield was 72% and the enantiomeric excess was 97%. 2a, white solid is added into the mixture,¹H NMR(400MHz,Chloroform-d)7.39–7.24(m,5H),4.67(dq,J＝8.4,6.8Hz,1H),4.55(s,1H),1.57(d,J＝6.8Hz,3H),1.31(s,9H)；¹³C NMR(101MHz,Chloroform-d)143.8,129.0,127.7,126.1,60.0,54.7,25.9,24.4.

example 32

2a(R¹＝Ph,R²＝CH₃,R³t-Bu) preparation

To a 10mL Schlenck tube, phosphine ligand L14(0.002mmol), nickel acetate tetrahydrate (0.5mg,0.002mmol) and N-sulfonimide 1a (0.4mmol) were added, the system was passed through a vacuum line, replaced with nitrogen gas 3 times, 1mL of trifluoroethanol solvent was added, the autoclave was charged, after 6 times of hydrogen replacement, the initial hydrogen pressure was set to 45bar, and the reaction was stirred at room temperature for 24 hours. Cooling, carefully venting, opening the autoclave, removing the vial, draining the solvent, detecting the conversion by NMR, and performing column chromatography to obtain the product. The yield was 79% and the enantiomeric excess was 91%. 2a, white solid is added into the mixture,¹H NMR(400MHz,Chloroform-d)7.39–7.24(m,5H),4.67(dq,J＝8.4,6.8Hz,1H),4.55(s,1H),1.57(d,J＝6.8Hz,3H),1.31(s,9H)；¹³C NMR(101MHz,Chloroform-d)143.8,129.0,127.7,126.1,60.0,54.7,25.9,24.4.

example 33

2a(R¹＝Ph,R²＝CH₃,R³t-Bu) preparation

To a 10mL Schlenck tube, phosphine ligand L15(0.002mmol), nickel acetate tetrahydrate (0.5mg,0.002mmol) and N-sulfonimide 1a (0.4mmol) were added, the system was passed through a vacuum line, replaced with nitrogen gas 3 times, 1mL of trifluoroethanol solvent was added, the autoclave was charged, after 6 times of replacement with hydrogen gas, the initial hydrogen pressure was made 10bar, and the reaction was stirred at room temperature for 24 hours. Cooling, carefully venting, opening the autoclave, removing the vial, draining the solvent, detecting the conversion by NMR, and performing column chromatography to obtain the product. The yield was 87% and the enantiomeric excess was 79%. 2a, white solid is added into the mixture,¹H NMR(400MHz,Chloroform-d)7.39–7.24(m,5H),4.67(dq,J＝8.4,6.8Hz,1H),4.55(s,1H),1.57(d,J＝6.8Hz,3H),1.31(s,9H)；¹³C NMR(101MHz,Chloroform-d)143.8,129.0,127.7,126.1,60.0,54.7,25.9,24.4.

example 34

2a(R¹＝Ph,R²＝CH₃,R³t-Bu) preparation

To a 10mL Schlenck tube, phosphine ligand L16(0.002mmol), nickel acetate tetrahydrate (0.5mg,0.002mmol) and N-sulfonimide 1a (0.4mmol) were added, the system was passed through a vacuum line, replaced with nitrogen gas 3 times, 1mL of trifluoroethanol solvent was added, the autoclave was charged, after 6 times of hydrogen replacement, the initial hydrogen pressure was made 5bar, and the reaction was stirred at room temperature for 24 hours. Cooling, carefully venting, opening the autoclave, removing the vial, draining the solvent, detecting the conversion by NMR, and performing column chromatography to obtain the product. The yield was 79% and the enantiomeric excess was 59%. 2a, white solid is added into the mixture,¹H NMR(400MHz,Chloroform-d)7.39–7.24(m,5H),4.67(dq,J＝8.4,6.8Hz,1H),4.55(s,1H),1.57(d,J＝6.8Hz,3H),1.31(s,9H)；¹³C NMR(101MHz,Chloroform-d)143.8,129.0,127.7,126.1,60.0,54.7,25.9,24.4.

example 35

2a(R¹＝Ph,R²＝CH₃,R³t-Bu) preparation

To a 10mL Schlenck tube, phosphine ligand L17(0.002mmol), nickel acetate tetrahydrate (0.5mg,0.002mmol) and N-sulfonimide 1a (0.4mmol) were added, the system was passed through a vacuum line, replaced with nitrogen gas 3 times, 1mL of trifluoroethanol solvent was added, the autoclave was charged, after 6 times of hydrogen replacement, the initial hydrogen pressure was made 1bar, and the reaction was stirred at room temperature for 1 hour. Cooling, carefully venting, opening the autoclave, removing the vial, draining the solvent, detecting the conversion by NMR, and performing column chromatography to obtain the product. The yield was 61% and the enantiomeric excess was 69%. 2a, white solid is added into the mixture,¹H NMR(400MHz,Chloroform-d)7.39–7.24(m,5H),4.67(dq,J＝8.4,6.8Hz,1H),4.55(s,1H),1.57(d,J＝6.8Hz,3H),1.31(s,9H)；¹³C NMR(101MHz,Chloroform-d)143.8,129.0,127.7,126.1,60.0,54.7,25.9,24.4.

example 36

2a(R¹＝Ph,R²＝CH₃,R³t-Bu) preparation

To a 10mL Schlenck tube, phosphine ligand L8(0.002 mmo) was addedl), nickel acetate (0.5mg,0.002mmol) and N-sulfonimide 1a (0.4mmol), the system was passed through a vacuum line, replaced with nitrogen gas 3 times, 1mL of trifluoroethanol solvent was added, the autoclave was charged, after 6 times of hydrogen replacement, the initial hydrogen pressure was made 10bar, and the reaction was stirred at 50 ℃ for 24 hours. Cooling, carefully venting, opening the autoclave, removing the vial, draining the solvent, detecting the conversion by NMR, and performing column chromatography to obtain the product. The yield was 99% and the enantiomeric excess was 99%. 2a, white solid is added into the mixture,¹H NMR(400MHz,Chloroform-d)7.39–7.24(m,5H),4.67(dq,J＝8.4,6.8Hz,1H),4.55(s,1H),1.57(d,J＝6.8Hz,3H),1.31(s,9H)；¹³C NMR(101MHz,Chloroform-d)143.8,129.0,127.7,126.1,60.0,54.7,25.9,24.4.

example 37

2a(R¹＝Ph,R²＝CH₃,R³t-Bu) preparation

Phosphine ligand L8(0.002mmol), nickel chloride (0.002mmol) and N-sulfonimide 1a (0.4mmol) were added to a 10mL Schlenck tube, the system was passed through a vacuum line, replaced with nitrogen gas 3 times, 1mL of trifluoroethanol solvent was added, the autoclave was charged, after 6 times of hydrogen replacement, the initial hydrogen pressure was made 10bar, and the reaction was stirred at 50 ℃ for 24 hours. Cooling, carefully venting, opening the autoclave, removing the vial, draining the solvent, detecting the conversion by NMR, and performing column chromatography to obtain the product. The yield was 54% and the enantiomeric excess was 83%. 2a, white solid is added into the mixture,¹H NMR(400MHz,Chloroform-d)7.39–7.24(m,5H),4.67(dq,J＝8.4,6.8Hz,1H),4.55(s,1H),1.57(d,J＝6.8Hz,3H),1.31(s,9H)；¹³C NMR(101MHz,Chloroform-d)143.8,129.0,127.7,126.1,60.0,54.7,25.9,24.4.

example 38

2a(R¹＝Ph,R²＝CH₃,R³t-Bu) preparation

Phosphine ligand L8(0.002mmol), nickel bromide (0.002mmol) and N-sulfonimide 1a (0.4mmol) were added to a 10mL Schlenck tube, the system was passed through a vacuum line, replaced with nitrogen 3 times, 1mL trifluoroethanol solvent was added, the autoclave was charged, and after 6 times replacement with hydrogen, initial hydrogen was allowed to flow throughThe reaction was stirred at 50 ℃ for 24 hours under a pressure of 10 bar. Cooling, carefully venting, opening the autoclave, removing the vial, draining the solvent, detecting the conversion by NMR, and performing column chromatography to obtain the product. The yield was 63% and the enantiomeric excess was 88%. 2a, white solid is added into the mixture,¹H NMR(400MHz,Chloroform-d)7.39–7.24(m,5H),4.67(dq,J＝8.4,6.8Hz,1H),4.55(s,1H),1.57(d,J＝6.8Hz,3H),1.31(s,9H)；¹³C NMR(101MHz,Chloroform-d)143.8,129.0,127.7,126.1,60.0,54.7,25.9,24.4.

example 39

2a(R¹＝Ph,R²＝CH₃,R³t-Bu) preparation

Phosphine ligand L8(0.002mmol), nickel sulfate hexahydrate (0.002mmol) and N-sulfonimide 1a (0.4mmol) were added to a 10mL Schlenck tube, the system was passed through a vacuum line, replaced with nitrogen gas 3 times, 1mL of trifluoroethanol solvent was added, the autoclave was charged, after 6 times of hydrogen replacement, the initial hydrogen pressure was made 10bar, and the reaction was stirred at 50 ℃ for 24 hours. Cooling, carefully venting, opening the autoclave, removing the vial, draining the solvent, detecting the conversion by NMR, and performing column chromatography to obtain the product. The yield was 76% and the enantiomeric excess was 90%. 2a, white solid is added into the mixture,¹H NMR(400MHz,Chloroform-d)7.39–7.24(m,5H),4.67(dq,J＝8.4,6.8Hz,1H),4.55(s,1H),1.57(d,J＝6.8Hz,3H),1.31(s,9H)；¹³C NMR(101MHz,Chloroform-d)143.8,129.0,127.7,126.1,60.0,54.7,25.9,24.4.

example 40

2a(R¹＝Ph,R²＝CH₃,R³t-Bu) preparation

Phosphine ligand L8(0.002mmol), nickel trifluoromethanesulfonate (0.002mmol) and N-sulfonimide 1a (0.4mmol) were added to a 10mL Schlenck tube, the system was passed through a vacuum line, replaced with nitrogen gas 3 times, 1mL of trifluoroethanol solvent was added, the autoclave was charged, and after 6 times of replacement with hydrogen gas, the initial hydrogen pressure was set to 10bar, and the reaction was stirred at 50 ℃ for 24 hours. Cooling, carefully venting, opening the autoclave, removing the vial, draining the solvent, detecting the conversion by NMR, and performing column chromatography to obtain the product. Product produced by birthThe rate was 57% and the enantiomeric excess was 78%. 2a, white solid is added into the mixture,¹H NMR(400MHz,Chloroform-d)7.39–7.24(m,5H),4.67(dq,J＝8.4,6.8Hz,1H),4.55(s,1H),1.57(d,J＝6.8Hz,3H),1.31(s,9H)；¹³C NMR(101MHz,Chloroform-d)143.8,129.0,127.7,126.1,60.0,54.7,25.9,24.4.

EXAMPLE 41

2a(R¹＝Ph,R²＝CH₃,R³t-Bu) preparation

Phosphine ligand L8(0.002mmol), nickel trifluoroacetate tetrahydrate (0.002mmol) and N-sulfonimide 1a (0.4mmol) were charged into a 10mL Schlenck tube, the system was passed through a vacuum line, replaced with nitrogen gas 3 times, 1mL of trifluoroethanol solvent was added, the autoclave was charged, after 6 times of hydrogen replacement, the initial hydrogen pressure was set to 10bar, and the reaction was stirred at 50 ℃ for 24 hours. Cooling, carefully venting, opening the autoclave, removing the vial, draining the solvent, detecting the conversion by NMR, and performing column chromatography to obtain the product. The yield was 85% and the enantiomeric excess was 93%. 2a, white solid is added into the mixture,¹H NMR(400MHz,Chloroform-d)7.39–7.24(m,5H),4.67(dq,J＝8.4,6.8Hz,1H),4.55(s,1H),1.57(d,J＝6.8Hz,3H),1.31(s,9H)；¹³C NMR(101MHz,Chloroform-d)143.8,129.0,127.7,126.1,60.0,54.7,25.9,24.4.

example 42

2a(R¹＝Ph,R²＝CH₃,R³t-Bu) preparation

To a 10mL Schlenck tube, phosphine ligand L8(0.002mmol), nickel acetate tetrahydrate (0.5mg,0.002mmol) and N-sulfonimide 1a (0.4mmol) were added, the system was passed through a vacuum line, replaced with nitrogen gas 3 times, 1mL of tetrahydrofuran solvent was added, the autoclave was charged, after 6 times of replacement with hydrogen gas, the initial hydrogen pressure was made 10bar, and the reaction was stirred at 50 ℃ for 24 hours. Cooling, carefully venting, opening the autoclave, removing the vial, draining the solvent, detecting the conversion by NMR, and performing column chromatography to obtain the product. The yield was 83% and the enantiomeric excess was 75%. 2a, white solid is added into the mixture,¹H NMR(400MHz,Chloroform-d)7.39–7.24(m,5H),4.67(dq,J＝8.4,6.8Hz,1H),4.55(s,1H),1.57(d,J＝6.8Hz,3H),1.31(s,9H)；¹³C NMR(101MHz,Chloroform-d)143.8,129.0,127.7,126.1,60.0,54.7,25.9,24.4.

example 43

2a(R¹＝Ph,R²＝CH₃,R³t-Bu) preparation

To a 10mL Schlenck tube, phosphine ligand L8(0.002mmol), nickel acetate tetrahydrate (0.5mg,0.002mmol) and N-sulfonimide 1a (0.4mmol) were added, the system was passed through a vacuum line, replaced with nitrogen gas 3 times, 1mL of methanol solvent was added, the autoclave was charged, after 6 times of replacement with hydrogen gas, the initial hydrogen pressure was made 10bar, and the reaction was stirred at 50 ℃ for 24 hours. Cooling, carefully venting, opening the autoclave, removing the vial, draining the solvent, detecting the conversion by NMR, and performing column chromatography to obtain the product. The yield was 94% and the enantiomeric excess was 98%. 2a, white solid is added into the mixture,¹H NMR(400MHz,Chloroform-d)7.39–7.24(m,5H),4.67(dq,J＝8.4,6.8Hz,1H),4.55(s,1H),1.57(d,J＝6.8Hz,3H),1.31(s,9H)；¹³C NMR(101MHz,Chloroform-d)143.8,129.0,127.7,126.1,60.0,54.7,25.9,24.4.

example 44

2a(R¹＝Ph,R²＝CH₃,R³t-Bu) preparation

To a 10mL Schlenck tube, phosphine ligand L8(0.002mmol), nickel acetate tetrahydrate (0.5mg,0.002mmol) and N-sulfonimide 1a (0.4mmol) were added, the system was passed through a vacuum line, replaced with nitrogen gas 3 times, 1mL of ethanol solvent was added, the autoclave was charged, after 6 times of replacement with hydrogen gas, the initial hydrogen pressure was made 10bar, and the reaction was stirred at 50 ℃ for 24 hours. Cooling, carefully venting, opening the autoclave, removing the vial, draining the solvent, detecting the conversion by NMR, and performing column chromatography to obtain the product. The yield was 95% and the enantiomeric excess was 91%. 2a, white solid is added into the mixture,¹H NMR(400MHz,Chloroform-d)7.39–7.24(m,5H),4.67(dq,J＝8.4,6.8Hz,1H),4.55(s,1H),1.57(d,J＝6.8Hz,3H),1.31(s,9H)；¹³C NMR(101MHz,Chloroform-d)143.8,129.0,127.7,126.1,60.0,54.7,25.9,24.4.

example 45

2a(R¹＝Ph,R²＝CH₃,R³t-Bu) preparation

Phosphine ligand L8(0.002mmol), nickel acetate tetrahydrate (0.5mg,0.002mmol) and N-sulfonimide 1a (0.4mmol) were added to a 10mL Schlenck tube, the system was passed through a vacuum line, replaced with nitrogen 3 times, 1mL of isopropanol solvent was added, the autoclave was charged, after 6 times of replacement with hydrogen, the initial hydrogen pressure was 10bar, and the reaction was stirred at 50 ℃ for 24 hours. Cooling, carefully venting, opening the autoclave, removing the vial, draining the solvent, detecting the conversion by NMR, and performing column chromatography to obtain the product. The yield was 86% with an enantiomeric excess of 90%. 2a, white solid is added into the mixture,¹H NMR(400MHz,Chloroform-d)7.39–7.24(m,5H),4.67(dq,J＝8.4,6.8Hz,1H),4.55(s,1H),1.57(d,J＝6.8Hz,3H),1.31(s,9H)；¹³C NMR(101MHz,Chloroform-d)143.8,129.0,127.7,126.1,60.0,54.7,25.9,24.4.

example 46

2a(R¹＝Ph,R²＝CH₃,R³t-Bu) preparation

To a 10mL Schlenck tube, phosphine ligand L8(0.002mmol), nickel acetate tetrahydrate (0.5mg,0.002mmol) and N-sulfonimide 1a (0.4mmol) were added, the system was passed through a vacuum line, replaced with nitrogen gas 3 times, 1mL of acetone solvent was added, the autoclave was charged, after 6 times of hydrogen replacement, the initial hydrogen pressure was 10bar, and the reaction was stirred at 50 ℃ for 24 hours. Cooling, carefully venting, opening the autoclave, removing the vial, draining the solvent, detecting the conversion by NMR, and performing column chromatography to obtain the product. The yield was 64% and the enantiomeric excess was 84%. 2a, white solid is added into the mixture,¹H NMR(400MHz,Chloroform-d)7.39–7.24(m,5H),4.67(dq,J＝8.4,6.8Hz,1H),4.55(s,1H),1.57(d,J＝6.8Hz,3H),1.31(s,9H)；¹³C NMR(101MHz,Chloroform-d)143.8,129.0,127.7,126.1,60.0,54.7,25.9,24.4.

example 47

2a(R¹＝Ph,R²＝CH₃,R³t-Bu) preparation

In a 10mL Schlenck tube,phosphine ligand L8(0.002mmol), nickel acetate tetrahydrate (0.5mg,0.002mmol) and N-sulfonimide 1a (0.4mmol) were added, the system was passed through a vacuum line, replaced with nitrogen gas 3 times, 1mL of acetonitrile solvent was added, the mixture was charged into an autoclave, replaced with hydrogen gas 6 times, the initial hydrogen pressure was made 10bar, and the reaction was stirred at 50 ℃ for 36 hours. Cooling, carefully venting, opening the autoclave, removing the vial, draining the solvent, detecting the conversion by NMR, and performing column chromatography to obtain the product. The yield was 65% with an enantiomeric excess of 68%. 2a, white solid is added into the mixture,¹H NMR(400MHz,Chloroform-d)7.39–7.24(m,5H),4.67(dq,J＝8.4,6.8Hz,1H),4.55(s,1H),1.57(d,J＝6.8Hz,3H),1.31(s,9H)；¹³C NMR(101MHz,Chloroform-d)143.8,129.0,127.7,126.1,60.0,54.7,25.9,24.4.

example 48

2a(R¹＝Ph,R²＝CH₃,R³t-Bu) preparation

Phosphine ligand L8(0.002mmol), nickel acetate tetrahydrate (0.5mg,0.002mmol) and N-sulfonimide 1a (0.4mmol) were added to a 10mL Schlenck tube, the system was passed through a vacuum line, replaced with nitrogen 3 times, 1Ml DMF solvent was added, the autoclave was charged, after 6 hydrogen replacements, the initial hydrogen pressure was 10bar, and the reaction was stirred at 50 ℃ for 24 hours. Cooling, carefully venting, opening the autoclave, removing the vial, draining the solvent, detecting the conversion by NMR, and performing column chromatography to obtain the product. The yield was 77% with an enantiomeric excess of 63%. 2a, white solid is added into the mixture,¹H NMR(400MHz,Chloroform-d)7.39–7.24(m,5H),4.67(dq,J＝8.4,6.8Hz,1H),4.55(s,1H),1.57(d,J＝6.8Hz,3H),1.31(s,9H)；¹³C NMR(101MHz,Chloroform-d)143.8,129.0,127.7,126.1,60.0,54.7,25.9,24.4.

example 49

2a(R¹＝Ph,R²＝CH₃,R³t-Bu) preparation

To a 10mL Schlenck tube, phosphine ligand L8(0.002mmol), nickel acetate tetrahydrate (0.5mg,0.002mmol) and N-sulfonimide 1a (0.4mmol) were added, the system was passed through a vacuum line, replaced with nitrogen gas 3 times, 1mL of toluene solvent was added, the autoclave was charged, and the mixture was passed through a Schlenck tubeAfter 6 hydrogen replacements, the initial hydrogen pressure was brought to 10bar and the reaction was stirred at 50 ℃ for 24 hours. Cooling, carefully venting, opening the autoclave, removing the vial, draining the solvent, detecting the conversion by NMR, and performing column chromatography to obtain the product. The yield was 98% and the enantiomeric excess was 89%. 2a, white solid is added into the mixture,¹H NMR(400MHz,Chloroform-d)7.39–7.24(m,5H),4.67(dq,J＝8.4,6.8Hz,1H),4.55(s,1H),1.57(d,J＝6.8Hz,3H),1.31(s,9H)；¹³C NMR(101MHz,Chloroform-d)143.8,129.0,127.7,126.1,60.0,54.7,25.9,24.4.

example 50

2a(R¹＝Ph,R²＝CH₃,R³t-Bu) preparation

To a 10mL Schlenck tube, phosphine ligand L8(0.002mmol), nickel acetate tetrahydrate (0.5mg,0.002mmol) and N-sulfonimide 1a (0.4mmol) were added, the system was passed through a vacuum line, replaced with nitrogen gas 3 times, 1mL of dichloromethane solvent was added, the autoclave was charged, after 6 times of replacement with hydrogen gas, the initial hydrogen pressure was made 10bar, and the reaction was stirred at 50 ℃ for 24 hours. Cooling, carefully venting, opening the autoclave, removing the vial, draining the solvent, detecting the conversion by NMR, and performing column chromatography to obtain the product. The yield was 71% with an enantiomeric excess of 76%. 2a, white solid is added into the mixture,¹H NMR(400MHz,Chloroform-d)7.39–7.24(m,5H),4.67(dq,J＝8.4,6.8Hz,1H),4.55(s,1H),1.57(d,J＝6.8Hz,3H),1.31(s,9H)；¹³C NMR(101MHz,Chloroform-d)143.8,129.0,127.7,126.1,60.0,54.7,25.9,24.4.

example 51

2a(R¹＝Ph,R²＝CH₃,R³t-Bu) preparation

To a 10mL Schlenck tube, phosphine ligand L8(0.002mmol), nickel acetate tetrahydrate (0.5mg,0.002mmol) and N-sulfonimide 1a (0.4mmol) were added, the system was passed through a vacuum line, replaced with nitrogen gas 3 times, 1mL trifluoroethanol/dichloromethane (1/1) solvent was added, the autoclave was charged, after 6 hydrogen replacements, the initial hydrogen pressure was 10bar, and the reaction was stirred at 50 ℃ for 24 hours. Cooling, carefully venting, opening the autoclave, removing the vial,and (4) draining the solvent, detecting the conversion rate by NMR, and carrying out column chromatography to obtain the product. The yield was 62% with an enantiomeric excess of 76%. 2a, white solid is added into the mixture,¹H NMR(400MHz,Chloroform-d)7.39–7.24(m,5H),4.67(dq,J＝8.4,6.8Hz,1H),4.55(s,1H),1.57(d,J＝6.8Hz,3H),1.31(s,9H)；¹³C NMR(101MHz,Chloroform-d)143.8,129.0,127.7,126.1,60.0,54.7,25.9,24.4.

example 52

2a(R¹＝Ph,R²＝CH₃,R³t-Bu) preparation

To a 10mL Schlenck tube, phosphine ligand L8(0.002mmol), nickel acetate tetrahydrate (0.5mg,0.002mmol) and N-sulfonimide 1a (0.4mmol) were added, the system was passed through a vacuum line, replaced with nitrogen gas 3 times, 1mL trifluoroethanol/diethyl ether (1/1) solvent was added, the autoclave was charged, after 6 hydrogen replacements, the initial hydrogen pressure was 10bar, and the reaction was stirred at 50 ℃ for 24 hours. Cooling, carefully venting, opening the autoclave, removing the vial, draining the solvent, detecting the conversion by NMR, and performing column chromatography to obtain the product. The yield was 72% and the enantiomeric excess was 85%. 2a, white solid is added into the mixture,¹H NMR(400MHz,Chloroform-d)7.39–7.24(m,5H),4.67(dq,J＝8.4,6.8Hz,1H),4.55(s,1H),1.57(d,J＝6.8Hz,3H),1.31(s,9H)；¹³C NMR(101MHz,Chloroform-d)143.8,129.0,127.7,126.1,60.0,54.7,25.9,24.4.

example 53

2a(R¹＝Ph,R²＝CH₃,R³t-Bu) preparation

To a 10mL Schlenck tube, phosphine ligand L8(0.002mmol), nickel acetate tetrahydrate (0.5mg,0.002mmol) and N-sulfonimide 1a (0.4mmol) were added, the system was passed through a vacuum line, replaced with nitrogen gas 3 times, 1mL trifluoroethanol/ethanol (1/1) solvent was added, the autoclave was charged, after 6 hydrogen replacements, the initial hydrogen pressure was 10bar, and the reaction was stirred at 50 ℃ for 24 hours. Cooling, carefully venting, opening the autoclave, removing the vial, draining the solvent, detecting the conversion by NMR, and performing column chromatography to obtain the product. The yield was 92% and the enantiomeric excess was 91%. 2a, white solid is added into the mixture,¹H NMR(400MHz,Chloroform-d)7.39–7.24(m,5H),4.67(dq,J＝8.4,6.8Hz,1H),4.55(s,1H),1.57(d,J＝6.8Hz,3H),1.31(s,9H)；¹³C NMR(101MHz,Chloroform-d)143.8,129.0,127.7,126.1,60.0,54.7,25.9,24.4.

example 54

2a(R¹＝Ph,R²＝CH₃,R³t-Bu) preparation

To a 10mL Schlenck tube, phosphine ligand L8(0.002mmol), nickel acetate tetrahydrate (0.5mg,0.002mmol) and N-sulfonimide 1a (0.4mmol) were added, the system was passed through a vacuum line, replaced with nitrogen gas 3 times, 1mL trifluoroethanol/ethanol (1/8) solvent was added, the autoclave was charged, after 6 hydrogen replacements, the initial hydrogen pressure was 10bar, and the reaction was stirred at 50 ℃ for 24 hours. Cooling, carefully venting, opening the autoclave, removing the vial, draining the solvent, detecting the conversion by NMR, and performing column chromatography to obtain the product. The yield was 95% and the enantiomeric excess was 92%. 2a, white solid is added into the mixture,¹H NMR(400MHz,Chloroform-d)7.39–7.24(m,5H),4.67(dq,J＝8.4,6.8Hz,1H),4.55(s,1H),1.57(d,J＝6.8Hz,3H),1.31(s,9H)；¹³C NMR(101MHz,Chloroform-d)143.8,129.0,127.7,126.1,60.0,54.7,25.9,24.4.

example 55

2a(R¹＝Ph,R²＝CH₃,R³t-Bu) preparation

To a 10mL Schlenck tube, phosphine ligand L8(0.002mmol), nickel acetate tetrahydrate (0.5mg,0.002mmol) and N-sulfonimide 1a (0.4mmol) were added, the system was passed through a vacuum line, replaced with nitrogen gas 3 times, 1mL of toluene solvent was added, the autoclave was charged, after 6 times of replacement with hydrogen gas, the initial hydrogen pressure was made 30bar, and the reaction was stirred at 0 ℃ for 24 hours. Cooling, carefully venting, opening the autoclave, removing the vial, draining the solvent, detecting the conversion by NMR, and performing column chromatography to obtain the product. The yield was 98% and the enantiomeric excess was 99%. 2a, white solid is added into the mixture,¹H NMR(400MHz,Chloroform-d)7.39–7.24(m,5H),4.67(dq,J＝8.4,6.8Hz,1H),4.55(s,1H),1.57(d,J＝6.8Hz,3H),1.31(s,9H)；¹³C NMR(101MHz,Chloroform-d)143.8,129.0,127.7,126.1,60.0,54.7,25.9,24.4.

example 56

2a(R¹＝Ph,R²＝CH₃,R³t-Bu) preparation

To a 10mL Schlenck tube, phosphine ligand L8(0.002mmol), nickel acetate tetrahydrate (0.5mg,0.002mmol) and N-sulfonimide 1a (0.8mmol, S/C ═ 400) were added, the system was passed through a vacuum line, replaced with nitrogen gas 3 times, 1mL of trifluoroethanol solvent was added, the autoclave was charged, after 6 times replacement with hydrogen gas, the initial hydrogen pressure was set to 10bar, and the reaction was stirred at 50 ℃ for 24 hours. Cooling, carefully venting, opening the autoclave, removing the vial, draining the solvent, detecting the conversion by NMR, and performing column chromatography to obtain the product. The yield was 99% and the enantiomeric excess was 97%. 2a, white solid is added into the mixture,¹H NMR(400MHz,Chloroform-d)7.39–7.24(m,5H),4.67(dq,J＝8.4,6.8Hz,1H),4.55(s,1H),1.57(d,J＝6.8Hz,3H),1.31(s,9H)；¹³C NMR(101MHz,Chloroform-d)143.8,129.0,127.7,126.1,60.0,54.7,25.9,24.4.

example 57

2a(R¹＝Ph,R²＝CH₃,R³t-Bu) preparation

To a 10mL Schlenck tube, phosphine ligand L8(0.002mmol), nickel acetate tetrahydrate (0.5mg,0.002mmol) and N-sulfonimide 1a (2.0mmol, S/C ═ 1000) were added, the system was passed through a vacuum line, replaced with nitrogen gas 3 times, 1mL of trifluoroethanol solvent was added, the autoclave was charged, after 6 times replacement with hydrogen gas, the initial hydrogen pressure was set to 10bar, and the reaction was stirred at 50 ℃ for 24 hours. Cooling, carefully venting, opening the autoclave, removing the vial, draining the solvent, detecting the conversion by NMR, and performing column chromatography to obtain the product. The yield was 99% and the enantiomeric excess was 97%. 2a, white solid is added into the mixture,¹H NMR(400MHz,Chloroform-d)7.39–7.24(m,5H),4.67(dq,J＝8.4,6.8Hz,1H),4.55(s,1H),1.57(d,J＝6.8Hz,3H),1.31(s,9H)；¹³C NMR(101MHz,Chloroform-d)143.8,129.0,127.7,126.1,60.0,54.7,25.9,24.4.

example 58

2a(R¹＝Ph,R²＝CH₃,R³t-Bu) preparation

To a 10mL Schlenck tube, phosphine ligand L8(0.002mmol), nickel acetate tetrahydrate (0.5mg,0.002mmol) and N-sulfonimide 1a (4.0mmol, S/C ═ 2000) were added, the system was passed through a vacuum line, replaced with nitrogen gas 3 times, 1mL of trifluoroethanol solvent was added, the autoclave was charged, after 6 times replacement with hydrogen gas, the initial hydrogen pressure was set to 10bar, and the reaction was stirred at 50 ℃ for 24 hours. Cooling, carefully venting, opening the autoclave, removing the vial, draining the solvent, detecting the conversion by NMR, and performing column chromatography to obtain the product. The yield was 99% and the enantiomeric excess was 97%. 2a, white solid is added into the mixture,¹H NMR(400MHz,Chloroform-d)7.39–7.24(m,5H),4.67(dq,J＝8.4,6.8Hz,1H),4.55(s,1H),1.57(d,J＝6.8Hz,3H),1.31(s,9H)；¹³C NMR(101MHz,Chloroform-d)143.8,129.0,127.7,126.1,60.0,54.7,25.9,24.4.

example 59

2a(R¹＝Ph,R²＝CH₃,R³t-Bu) preparation

To a 10mL Schlenck tube, phosphine ligand L8(0.002mmol), nickel acetate tetrahydrate (0.5mg,0.002mmol) and N-sulfonimide 1a (10.0mmol, S/C ═ 5000) were added, the system was passed through a vacuum line, replaced with nitrogen gas 3 times, 1mL of trifluoroethanol solvent was added, the autoclave was charged, after 6 times of replacement with hydrogen gas, the initial hydrogen pressure was made 10bar, and the reaction was stirred at 50 ℃ for 24 hours. Cooling, carefully venting, opening the autoclave, removing the vial, draining the solvent, detecting the conversion by NMR, and performing column chromatography to obtain the product. The yield was 99% and the enantiomeric excess was 97%. 2a, white solid is added into the mixture,¹H NMR(400MHz,Chloroform-d)7.39–7.24(m,5H),4.67(dq,J＝8.4,6.8Hz,1H),4.55(s,1H),1.57(d,J＝6.8Hz,3H),1.31(s,9H)；¹³C NMR(101MHz,Chloroform-d)143.8,129.0,127.7,126.1,60.0,54.7,25.9,24.4.

example 60

2a(R¹＝Ph,R²＝CH₃,R³t-Bu) preparation

To a 10mL Schlenck tube, phosphine ligand L8 (0.0) was added02mmol), nickel acetate tetrahydrate (0.5mg,0.002mmol) and N-sulfonimide 1a (16.0mmol, S/C8000), the system was passed through a vacuum line, replaced with nitrogen gas 3 times, 1mL of trifluoroethanol solvent was added, the autoclave was charged, replaced with hydrogen gas 6 times, the initial hydrogen pressure was made 10bar, and the reaction was stirred at 50 ℃ for 24 hours. Cooling, carefully venting, opening the autoclave, removing the vial, draining the solvent, detecting the conversion by NMR, and performing column chromatography to obtain the product. The yield was 99% and the enantiomeric excess was 97%. 2a, white solid is added into the mixture,¹H NMR(400MHz,Chloroform-d)7.39–7.24(m,5H),4.67(dq,J＝8.4,6.8Hz,1H),4.55(s,1H),1.57(d,J＝6.8Hz,3H),1.31(s,9H)；¹³C NMR(101MHz,Chloroform-d)143.8,129.0,127.7,126.1,60.0,54.7,25.9,24.4.

example 61

2a(R¹＝Ph,R²＝CH₃,R³t-Bu) preparation

To a 10mL Schlenck tube, phosphine ligand L8(0.002mmol), nickel acetate tetrahydrate (0.5mg,0.002mmol) and N-sulfonimide 1a (20.0mmol, S/C ═ 10000) were added, the system was passed through a vacuum line, replaced with nitrogen gas 3 times, 1mL of trifluoroethanol solvent was added, the autoclave was charged, after 6 times of replacement with hydrogen gas, the initial hydrogen pressure was made 10bar, and the reaction was stirred at 50 ℃ for 24 hours. Cooling, carefully venting, opening the autoclave, removing the vial, draining the solvent, detecting the conversion by NMR, and performing column chromatography to obtain the product. The yield was 99% and the enantiomeric excess was 97%. 2a, white solid is added into the mixture,¹H NMR(400MHz,Chloroform-d)7.39–7.24(m,5H),4.67(dq,J＝8.4,6.8Hz,1H),4.55(s,1H),1.57(d,J＝6.8Hz,3H),1.31(s,9H)；¹³C NMR(101MHz,Chloroform-d)143.8,129.0,127.7,126.1,60.0,54.7,25.9,24.4.

example 62

2a(R¹＝Ph,R²＝CH₃,R³t-Bu) preparation

To a 10mL Schlenck tube, phosphine ligand L8(0.002mmol), nickel acetate tetrahydrate (0.5mg,0.002mmol) and N-sulfonimide 1a (60.0mmol, S/C. 30000) were added, the system was passed through a vacuum line, replaced with nitrogen gas 3 times, and 1mL of trifluoro toluene was addedThe ethanol solvent was charged into an autoclave, and after 6 times of hydrogen replacement, the initial hydrogen pressure was 10bar, and the reaction was stirred at 50 ℃ for 24 hours. Cooling, carefully venting, opening the autoclave, removing the vial, draining the solvent, detecting the conversion by NMR, and performing column chromatography to obtain the product. The yield was 99% and the enantiomeric excess was 97%. 2a, white solid is added into the mixture,¹H NMR(400MHz,Chloroform-d)7.39–7.24(m,5H),4.67(dq,J＝8.4,6.8Hz,1H),4.55(s,1H),1.57(d,J＝6.8Hz,3H),1.31(s,9H)；¹³C NMR(101MHz,Chloroform-d)143.8,129.0,127.7,126.1,60.0,54.7,25.9,24.4.

example 63

2a(R¹＝Ph,R²＝CH₃,R³t-Bu) preparation

To a 10mL Schlenck tube, phosphine ligand L8(0.002mmol), nickel acetate tetrahydrate (0.5mg,0.002mmol) and N-sulfonimide 1a (120.0mmol, S/C ═ 60000) were added, and the system was passed through a vacuum line, replaced with nitrogen gas 3 times, 1mL of trifluoroethanol solvent was added, the autoclave was charged, replaced with hydrogen gas 6 times, the initial hydrogen pressure was made 10bar, and the reaction was stirred at 50 ℃ for 24 hours. Cooling, carefully venting, opening the autoclave, removing the vial, draining the solvent, detecting the conversion by NMR, and performing column chromatography to obtain the product. The yield was 99% and the enantiomeric excess was 97%. 2a, white solid is added into the mixture,¹H NMR(400MHz,Chloroform-d)7.39–7.24(m,5H),4.67(dq,J＝8.4,6.8Hz,1H),4.55(s,1H),1.57(d,J＝6.8Hz,3H),1.31(s,9H)；¹³C NMR(101MHz,Chloroform-d)143.8,129.0,127.7,126.1,60.0,54.7,25.9,24.4.

example 64

2a(R¹＝Ph,R²＝CH₃,R³t-Bu) preparation

To a 10mL Schlenck tube, phosphine ligand L8(0.002mmol), nickel acetate tetrahydrate (0.5mg,0.002mmol) and N-sulfonimide 1a (200.0mmol, S/C ═ 100000) were added, and the system was passed through a vacuum line, replaced with nitrogen gas 3 times, 1mL of trifluoroethanol solvent was added, the autoclave was charged, replaced with hydrogen gas 6 times, the initial hydrogen pressure was made 10bar, and the reaction was stirred at 50 ℃ for 24 hours. Cooling, cautionAnd (4) discharging gas, opening the autoclave, taking out a small bottle, pumping out the solvent, detecting the conversion rate by NMR, and carrying out column chromatography to obtain the product. The yield was 96% and the enantiomeric excess was 97%. 2a, white solid is added into the mixture,¹H NMR(400MHz,Chloroform-d)7.39–7.24(m,5H),4.67(dq,J＝8.4,6.8Hz,1H),4.55(s,1H),1.57(d,J＝6.8Hz,3H),1.31(s,9H)；¹³C NMR(101MHz,Chloroform-d)143.8,129.0,127.7,126.1,60.0,54.7,25.9,24.4.

example 65

2a(R¹＝Ph,R²＝CH₃,R³t-Bu) preparation

To a 10mL Schlenck tube, phosphine ligand L8(0.002mmol), nickel acetate tetrahydrate (0.5mg,0.002mmol) and N-sulfonimide 1a (0.4mmol) were added, the system was passed through a vacuum line, replaced with nitrogen gas 3 times, 1mL of trifluoroethanol solvent was added, the autoclave was charged, after 6 times of hydrogen replacement, the initial hydrogen pressure was made 10bar, and the reaction was stirred at 50 ℃ for 24 hours. Cooling, carefully venting, opening the autoclave, removing the vial, draining the solvent, detecting the conversion by NMR, and performing column chromatography to obtain the product. The yield was 99% and the enantiomeric excess was 97%. 2a, white solid is added into the mixture,¹H NMR(400MHz,Chloroform-d)7.39–7.24(m,5H),4.67(dq,J＝8.4,6.8Hz,1H),4.55(s,1H),1.57(d,J＝6.8Hz,3H),1.31(s,9H)；¹³C NMR(101MHz,Chloroform-d)143.8,129.0,127.7,126.1,60.0,54.7,25.9,24.4.

example 66

2b(R¹＝2-Me-Ph,R²＝CH₃,R³t-Bu) preparation

To a 10mL Schlenck tube, phosphine ligand L8(0.002mmol), nickel acetate tetrahydrate (0.5mg,0.002mmol) and N-sulfonimide 1b (0.4mmol) were added, the system was passed through a vacuum line, replaced with nitrogen gas 3 times, 1mL of trifluoroethanol solvent was added, the autoclave was charged, after 6 times of hydrogen replacement, the initial hydrogen pressure was made 30bar, and the reaction was stirred at 70 ℃ for 24 hours. Cooling, carefully venting, opening the autoclave, removing the vial, draining the solvent, detecting the conversion by NMR, and performing column chromatography to obtain the product. The yield was 99% and the enantiomeric excess was 99%. 2b white solidThe body is provided with a plurality of grooves,¹H NMR(400MHz,Chloroform-d)7.31(d,J＝7.6Hz,1H),7.27–7.20(m,1H),7.19–7.10(m,2H),4.95–4.87(m,1H),4.69(d,J＝16.8Hz,1H),2.36(s,3H),1.50(d,J＝6.8Hz,3H),1.26(s,9H)；¹³C NMR(101MHz,Chloroform-d)142.4,134.1,130.9,127.4,126.9,125.2,59.9,50.8,25.6,24.3,19.3.

example 67

2c(R¹＝2-MeO-Ph,R²＝CH₃,R³t-Bu) preparation

To a 10mL Schlenck tube, phosphine ligand L8(0.002mmol), nickel acetate (7.04mg,0.04mmol) and N-sulfonimide 1c (6mmol) were added, the system was passed through a vacuum line, replaced with nitrogen gas 3 times, 4mL of trifluoroethanol solvent was added, the autoclave was charged, after 6 times of replacement with hydrogen gas, the initial hydrogen pressure was set to 50bar, and the reaction was stirred at 70 ℃ for 48 hours. Cooling, carefully venting, opening the autoclave, removing the vial, draining the solvent, detecting the conversion by NMR, and performing column chromatography to obtain the product. The yield was 99% and the enantiomeric excess was 98%. 2c, white solid, and (C),¹H NMR(400MHz,Chloroform-d)7.28–7.23(m,1H),7.13(dd,J＝7.2,1.6Hz,1H),6.96–6.89(m,2H),5.02(d,J＝10.0Hz,1H),4.65(dq,J＝10.0,6.8Hz,1H),3.88(s,3H),1.56(d,J＝6.8Hz,3H),1.28(s,9H)；¹³C NMR(101MHz,Chloroform-d)157.0,128.9,128.2,121.2,111.5,59.7,55.6,54.2,24.6,24.4.

example 68

2d(R¹＝2-F-Ph,R²＝CH₃,R³t-Bu) preparation

To a 10mL Schlenck tube, phosphine ligand L8(0.002mmol), nickel acetate tetrahydrate (0.5mg,0.002mmol) and N-sulfonimide 1d (0.1mmol) were added, the system was passed through a vacuum line, replaced with nitrogen gas 3 times, 1mL of trifluoroethanol solvent was added, the autoclave was charged, after 6 times of hydrogen replacement, the initial hydrogen pressure was made 30bar, and the reaction was stirred at 50 ℃ for 24 hours. Cooling, carefully venting, opening the autoclave, removing the vial, draining the solvent, detecting the conversion by NMR, and performing column chromatography to obtain the product. The yield was 96% and the enantiomeric excess was 97%. 2d, preparing a white solid, wherein the white solid is,¹H NMR(400MHz,Chloroform-d)7.30(td,J＝7.6,2.0Hz,1H),7.27–7.20(m,1H),7.12(td,J＝7.6,1.2Hz,1H),7.04(ddd,J＝10.8,8.2,1.2Hz,1H),4.87–4.75(m,2H),1.61–1.53(m,3H),1.29(s,9H)；¹³C NMR(101MHz,Chloroform-d)160.3(d,J＝146.0Hz),130.9(d,J＝13.3Hz),129.3(d,J＝8.4Hz),128.1(d,J＝4.8Hz),124.8(d,J＝3.5Hz),116.2(d,J＝21.9Hz),60.0,51.0,25.0,24.3；¹⁹F NMR(376MHz,Chloroform-d)-118.78.

example 69

2e(R¹＝2-Cl-Ph,R²＝CH₃,R³t-Bu) preparation

To a 10mL Schlenck tube, phosphine ligand L8(0.002mmol), nickel acetate tetrahydrate (0.5mg,0.002mmol) and N-sulfonimide 1e (0.1mmol) were added, the system was passed through a vacuum line, replaced with nitrogen gas 3 times, 1mL of trifluoroethanol solvent was added, the autoclave was charged, after 6 times of hydrogen replacement, the initial hydrogen pressure was made 30bar, and the reaction was stirred at 50 ℃ for 24 hours. Cooling, carefully venting, opening the autoclave, removing the vial, draining the solvent, detecting the conversion by NMR, and performing column chromatography to obtain the product. The yield was 99% and the enantiomeric excess was 99%. 2e, a white solid is added,¹H NMR(400MHz,Chloroform-d)7.38(dd,J＝7.6,1.6Hz,1H),7.34(dd,J＝8.0,1.2Hz,1H),7.31–7.24(m,1H),7.20(td,J＝7.6,1.6Hz,1H),5.04(dq,J＝9.2,6.8Hz,1H),4.93(d,J＝9.2Hz,1H),1.55(d,J＝6.8Hz,3H),1.29(s,9H).

example 70

2f(R¹＝3-Me-Ph,R²＝CH₃,R³t-Bu) preparation

To a 10mL Schlenck tube, phosphine ligand L8(0.002mmol), nickel acetate tetrahydrate (0.5mg,0.002mmol) and N-sulfonimide 1f (0.4mmol) were added, the system was passed through a vacuum line, replaced with nitrogen gas 3 times, 1mL of trifluoroethanol solvent was added, the autoclave was charged, after 6 times of hydrogen replacement, the initial hydrogen pressure was made 30bar, and the reaction was stirred at 50 ℃ for 24 hours. Cooling, carefully venting, opening the autoclave, removing the vial, draining the solvent, detecting the conversion by NMR, and performing column chromatography to obtain the product. The yield was 92%, enantiomeric excessThe value was 95%. 2f, white solid, and (C) in the presence of a catalyst,¹H NMR(400MHz,Chloroform-d)7.28–7.19(m,1H),7.15–7.04(m,3H),4.62(dt,J＝13.8,6.8Hz,1H),4.36(d,J＝8.8Hz,1H),2.35(s,3H),1.56(d,J＝6.8Hz,3H),1.32(s,9H)；¹³C NMR(101MHz,Chloroform-d)143.7,138.7,128.9,128.5,126.9,123.1,60.0,54.7,25.9,24.4,21.8.

example 71

2g(R¹＝3-MeO-Ph,R²＝CH₃,R³t-Bu) preparation

To a 10mL Schlenck tube, phosphine ligand L8(0.002mmol), nickel acetate tetrahydrate (0.5mg,0.002mmol) and 1g of N-sulfonimide (0.4mmol) were added, the system was passed through a vacuum line, replaced with nitrogen gas 3 times, 1mL of trifluoroethanol solvent was added, the autoclave was charged, after 6 times of hydrogen replacement, the initial hydrogen pressure was made 30bar, and the reaction was stirred at 50 ℃ for 24 hours. Cooling, carefully venting, opening the autoclave, removing the vial, draining the solvent, detecting the conversion by NMR, and performing column chromatography to obtain the product. The yield was 97% and the enantiomeric excess was 93%. 2g of a white solid, wherein the white solid is,¹H NMR(400MHz,Chloroform-d)7.25(t,J＝8.0Hz,1H),6.89(d,J＝7.6Hz,1H),6.88–6.85(m,1H),6.80(dd,J＝8.2,2.0Hz,1H),4.78(d,J＝9.2Hz,1H),4.62(dq,J＝9.2,6.8Hz,1H),3.80(s,3H),1.56(d,J＝6.8Hz,3H),1.30(s,9H)；¹³C NMR(101MHz,Chloroform-d)160.0,145.5,130.1,118.4,112.9,111.9,60.0,55.5,54.8,26.1,24.4.

example 72

2h(R¹＝3-F-Ph,R²＝CH₃,R³t-Bu) preparation

Phosphine ligand L8(0.002mmol), nickel acetate tetrahydrate (0.5mg,0.002mmol) and N-sulfonimide were added to a 10mL Schlenck tube and the system was passed through a vacuum line and replaced with nitrogen gas 3 times, 1mL of trifluoroethanol solvent was added, the autoclave was charged, after 6 times of replacement with hydrogen gas, the initial hydrogen pressure was made 30bar and the reaction was stirred at 50 ℃ for 24 hours. Cooling, carefully venting, opening the autoclave, removing the vial, draining the solvent, detecting the conversion by NMR, and performing column chromatography to obtain the product. The yield was 69%, enantiomeric excessThe amount was 86%. 2h, adding a white solid for 2h,¹H NMR(400MHz,Chloroform-d)7.31(td,J＝8.0,6.0Hz,1H),7.10(d,J＝7.6Hz,1H),7.03(dt,J＝10.0,2.0Hz,1H),7.00–6.88(m,1H),4.73–4.61(m,1H),4.45(d,J＝8.8Hz,1H),1.56(d,J＝6.8Hz,3H),1.32(s,9H)；¹³C NMR(101MHz,Chloroform-d)163.2(d,J＝247.6Hz),146.5,130.6(d,J＝8.1Hz),121.8,114.6(d,J＝21.3Hz),113.2(d,J＝22.1Hz),60.1,54.2,25.6,24.4；¹⁹F NMR(376MHz,Chloroform-d)-112.66.

example 73

2i(R¹＝3-Cl-Ph,R²＝CH₃,R³t-Bu) preparation

To a 10mL Schlenck tube, phosphine ligand L8(0.002mmol), nickel acetate tetrahydrate (0.5mg,0.002mmol) and N-sulfonimide 1i (0.1mmol) were added, the system was passed through a vacuum line, replaced with nitrogen gas 3 times, 1mL of trifluoroethanol solvent was added, the autoclave was charged, after 6 times of hydrogen replacement, the initial hydrogen pressure was made 30bar, and the reaction was stirred at 50 ℃ for 24 hours. Cooling, carefully venting, opening the autoclave, removing the vial, draining the solvent, detecting the conversion by NMR, and performing column chromatography to obtain the product. The yield was 61% and the enantiomeric excess was 89%. 2i, a white solid, and a white solid,¹H NMR(400MHz,Chloroform-d)7.33–7.14(m,4H),4.68–4.51(m,2H),1.54(d,J＝6.4Hz,3H),1.32(s,9H)；¹³C NMR(101MHz,Chloroform-d)146.0,134.8,130.3,127.9,126.4,124.4,60.1,54.3,25.6,24.4.

example 74

2j(R¹＝3-Br-Ph,R²＝CH₃,R³t-Bu) preparation

To a 10mL Schlenck tube, phosphine ligand L8(0.002mmol), nickel acetate tetrahydrate (0.5mg,0.002mmol) and N-sulfonimide 1j (0.1mmol) were added, the system was passed through a vacuum line, replaced with nitrogen gas 3 times, 1mL of trifluoroethanol solvent was added, the autoclave was charged, after 6 times of hydrogen replacement, the initial hydrogen pressure was made 30bar, and the reaction was stirred at 50 ℃ for 24 hours. Cooling, carefully venting, opening the autoclave, removing the vial, draining the solvent, detecting the conversion by NMR, and performing column chromatography to obtain the product. Product produced by birthThe ratio was 46% and the enantiomeric excess was 86%. 2j is a white solid, and the white solid,¹H NMR(400MHz,Chloroform-d)7.46(s,1H),7.40(d,J＝7.2Hz,1H),7.28–7.18(m,2H),4.63(dt,J＝14.4,6.8Hz,1H),4.41(d,J＝8.4Hz,1H),1.54(d,J＝6.8Hz,3H),1.32(s,9H)；¹³C NMR(101MHz,Chloroform-d)146.2,130.8,130.6,129.3,124.9,123.0,60.1,54.2,25.6,24.4.

example 75

2k(R¹＝4-Me-Ph,R²＝CH₃,R³t-Bu) preparation

To a 10mL Schlenck tube, phosphine ligand L8(0.002mmol), nickel acetate tetrahydrate (0.5mg,0.002mmol) and N-sulfonimide 1k (0.4mmol) were added, the system was passed through a vacuum line, replaced with nitrogen gas 3 times, 1mL of trifluoroethanol solvent was added, the autoclave was charged, after 6 times of hydrogen replacement, the initial hydrogen pressure was made 30bar, and the reaction was stirred at 50 ℃ for 24 hours. Cooling, carefully venting, opening the autoclave, removing the vial, draining the solvent, detecting the conversion by NMR, and performing column chromatography to obtain the product. The yield was 99% and the enantiomeric excess was 98%. 2k, the white solid is added into the solution,¹H NMR(400MHz,Chloroform-d)7.20(d,J＝8.4Hz,2H),7.15(d,J＝8.4Hz,2H),4.63(dt,J＝13.6,6.8Hz,1H),4.54(s,1H),2.33(s,3H),1.55(d,J＝6.8Hz,3H),1.31(s,9H)；¹³C NMR(101MHz,Chloroform-d)140.9,137.3,129.7,126.0,60.0,54.5,26.0,24.4,21.3.

example 76

2l(R¹＝4-MeO-Ph,R²＝CH₃,R³t-Bu) preparation

To a 10mL Schlenck tube, phosphine ligand L8(0.002mmol), nickel acetate tetrahydrate (0.5mg,0.002mmol) and 1L N-sulfonimide (0.4mmol) were added, the system was passed through a vacuum line, replaced with nitrogen gas 3 times, 1mL trifluoroethanol solvent was added, the autoclave was charged, after 6 times of hydrogen replacement, the initial hydrogen pressure was made 30bar, and the reaction was stirred at 50 ℃ for 24 hours. Cooling, carefully venting, opening the autoclave, removing the vial, draining the solvent, detecting the conversion by NMR, and performing column chromatography to obtain the product. The yield was 99% and the enantiomeric excess was 97%. 2l of a white solid, which is,¹H NMR(400MHz,Chloroform-d)7.24(d,J＝8.8Hz,2H),6.87(d,J＝8.8Hz,2H),4.68–4.57(m,1H),4.39(d,J＝8.8Hz,1H),3.80(s,3H),1.55(d,J＝6.8Hz,3H),1.31(s,9H)；¹³C NMR(101MHz,Chloroform-d)159.0,136.0,127.4,114.3,60.0,55.5,54.2,25.8,24.4.

example 77

2m(R¹＝4-Ph-Ph,R²＝CH₃,R³t-Bu) preparation

To a 10mL Schlenck tube, phosphine ligand L8(0.002mmol), nickel acetate tetrahydrate (0.5mg,0.002mmol) and N-sulfonimide (1 m) (0.1mmol) were added, the system was passed through a vacuum line, replaced with nitrogen gas 3 times, 1mL of trifluoroethanol solvent was added, the autoclave was charged, after 6 times of hydrogen replacement, the initial hydrogen pressure was made 30bar, and the reaction was stirred at 50 ℃ for 24 hours. Cooling, carefully venting, opening the autoclave, removing the vial, draining the solvent, detecting the conversion by NMR, and performing column chromatography to obtain the product. The yield was 99% and the enantiomeric excess was 94%. 2m of the white solid, wherein the white solid is,¹H NMR(400MHz,Chloroform-d)7.59(d,J＝8.0Hz,4H),7.48–7.38(m,4H),7.35(t,J＝7.2Hz,1H),4.76–4.68(m,2H),1.61(d,J＝6.4Hz,3H),1.35(s,9H)；¹³C NMR(101MHz,Chloroform-d)142.9,140.8,140.6,129.0,127.7,127.6,127.3,126.6,60.1,54.5,25.8,24.5.

example 78

2n(R¹＝4-F-Ph,R²＝CH₃,R³t-Bu) preparation

To a 10mL Schlenck tube, phosphine ligand L8(0.002mmol), nickel acetate tetrahydrate (0.5mg,0.002mmol) and N-sulfonimide 1N (0.1mmol) were added, the system was passed through a vacuum line, replaced with nitrogen gas 3 times, 1mL of trifluoroethanol solvent was added, the autoclave was charged, after 6 times of hydrogen replacement, the initial hydrogen pressure was made 30bar, and the reaction was stirred at 50 ℃ for 24 hours. Cooling, carefully venting, opening the autoclave, removing the vial, draining the solvent, detecting the conversion by NMR, and performing column chromatography to obtain the product. The yield was 84% with an enantiomeric excess of 83%. 2n is white solid, and the white solid is,¹H NMR(400MHz,Chloroform-d)7.29(ddd,J＝8.4,5.2,2.4Hz,2H),7.06–6.98(m,2H),4.72(d,J＝8.8Hz,1H),4.68–4.58(m,1H),1.54(d,J＝6.8Hz,3H),1.30(s,9H)；¹³C NMR(101MHz,Chloroform-d)162.2(d,J＝246.7Hz),139.8,127.9(d,J＝8.1Hz),115.8(d,J＝21.5Hz),60.0,54.1,25.7,24.4；¹⁹F NMR(376MHz,Chloroform-d)-115.54.

example 79

2o(R¹＝4-Cl-Ph,R²＝CH₃,R³t-Bu) preparation

To a 10mL Schlenck tube, phosphine ligand L8(0.002mmol), nickel acetate tetrahydrate (0.5mg,0.002mmol) and N-sulfonimide 1o (0.1mmol) were added, the system was passed through a vacuum line, replaced with nitrogen gas 3 times, 1mL of trifluoroethanol solvent was added, the autoclave was charged, after 6 times of hydrogen replacement, the initial hydrogen pressure was made 30bar, and the reaction was stirred at 50 ℃ for 24 hours. Cooling, carefully venting, opening the autoclave, removing the vial, draining the solvent, detecting the conversion by NMR, and performing column chromatography to obtain the product. The yield was 84% with an enantiomeric excess of 89%. 2o of a white solid, and the white solid,¹H NMR(400MHz,Chloroform-d)7.32(d,J＝8.4Hz,2H),7.28–7.23(m,2H),4.69–4.59(m,1H),4.52(d,J＝8.8Hz,1H),1.55(d,J＝6.8Hz,3H),1.31(s,9H)；¹³C NMR(101MHz,Chloroform-d)142.4,133.4,129.2,127.6,60.1,54.1,25.6,24.4.

example 80

2p(R¹＝4-Br-Ph,R²＝CH₃,R³t-Bu) preparation

To a 10mL Schlenck tube, phosphine ligand L8(0.002mmol), nickel acetate tetrahydrate (0.5mg,0.002mmol) and N-sulfonimide 1p (0.1mmol) were added, the system was passed through a vacuum line, replaced with nitrogen gas 3 times, 1mL of trifluoroethanol solvent was added, the autoclave was charged, after 6 times of hydrogen replacement, the initial hydrogen pressure was made 30bar, and the reaction was stirred at 50 ℃ for 24 hours. Cooling, carefully venting, opening the autoclave, removing the vial, draining the solvent, detecting the conversion by NMR, and performing column chromatography to obtain the product. The yield was 47% with an enantiomeric excess of 95%. 2p, the white solid is added into the solution,¹H NMR(400MHz,Chloroform-d)7.47(d,J＝8.4Hz,2H),7.20(d,J＝8.4Hz,2H),4.63(dt,J＝15.6,6.8Hz,1H),4.47(d,J＝8.8Hz,1H),1.54(d,J＝6.8Hz,3H),1.31(s,9H)；¹³C NMR(101MHz,Chloroform-d)142.9,132.1,127.9,121.5,60.1,54.2,25.6,24.4.

example 81

2q(R¹＝2,4-diMe-Ph,R²＝CH₃,R³t-Bu) preparation

To a 10mL Schlenck tube, phosphine ligand L8(0.002mmol), nickel acetate tetrahydrate (0.5mg,0.002mmol) and N-sulfonimide 1q (0.4mmol) were added, the system was passed through a vacuum line, replaced with nitrogen gas 3 times, 1mL of trifluoroethanol solvent was added, the autoclave was charged, after 6 times of hydrogen replacement, the initial hydrogen pressure was made 30bar, and the reaction was stirred at 70 ℃ for 24 hours. Cooling, carefully venting, opening the autoclave, removing the vial, draining the solvent, detecting the conversion by NMR, and performing column chromatography to obtain the product. The yield was 99% and the enantiomeric excess was 99.5%. 2q of a white solid, wherein the white solid is,¹H NMR(400MHz,Chloroform-d)7.15(d,J＝8.0Hz,1H),7.04(d,J＝8.0Hz,1H),6.96(s,1H),4.93–4.82(m,1H),4.20(d,J＝8.4Hz,1H),2.32(s,3H),2.30(s,3H),1.49(d,J＝6.8Hz,3H),1.27(s,9H)；¹³C NMR(101MHz,Chloroform-d)139.4,137.0,134.0,131.6,127.6,125.1,59.8,50.7,25.7,24.3,21.2,19.3.

example 82

2r(R¹＝3,4-diMe-Ph,R²＝CH₃,R³t-Bu) preparation

To a 10mL Schlenck tube, phosphine ligand L8(0.002mmol), nickel acetate tetrahydrate (0.5mg,0.002mmol) and N-sulfonimide 1r (0.4mmol) were added, the system was passed through a vacuum line, replaced with nitrogen gas 3 times, 1mL of trifluoroethanol solvent was added, the autoclave was charged, after 6 times of hydrogen replacement, the initial hydrogen pressure was made 30bar, and the reaction was stirred at 70 ℃ for 24 hours. Cooling, carefully venting, opening the autoclave, removing the vial, draining the solvent, detecting the conversion by NMR, and performing column chromatography to obtain the product. The yield was 91% and the enantiomeric excess was 94%. 2r of white solid, namely white solid,¹H NMR(400MHz,Chloroform-d)7.11(d,J＝7.6Hz,1H),7.08–7.01(m,2H),4.64–4.55(m,1H),4.38(s,1H),2.26(s,3H),2.24(s,3H),1.55(d,J＝6.8Hz,3H),1.32(s,9H)；¹³C NMR(101MHz,Chloroform-d)141.3,137.2,136.0,130.2,127.4,123.4,60.0,54.6,26.0,24.5,20.2,19.7.

example 83

2s(R¹＝2,5-diMeO-Ph,R²＝CH₃,R³t-Bu) preparation

To a 10mL Schlenck tube, phosphine ligand L8(0.002mmol), nickel acetate tetrahydrate (0.5mg,0.002mmol) and N-sulfonimide 1s (0.4mmol) were added, the system was passed through a vacuum line, replaced with nitrogen gas 3 times, 1mL of trifluoroethanol solvent was added, the autoclave was charged, after 6 times of hydrogen replacement, the initial hydrogen pressure was made 30bar, and the reaction was stirred at 70 ℃ for 24 hours. Cooling, carefully venting, opening the autoclave, removing the vial, draining the solvent, detecting the conversion by NMR, and performing column chromatography to obtain the product. The yield was 81% and the enantiomeric excess was 98%. 2s, the white solid is added into the solution,¹H NMR(400MHz,Chloroform-d)6.83(d,J＝8.8Hz,1H),6.76(dd,J＝8.8,2.8Hz,1H),6.72(d,J＝2.8Hz,1H),5.08(d,J＝10.0Hz,1H),4.60(dq,J＝10.0,6.8Hz,1H),3.83(s,3H),3.75(s,3H),1.54(d,J＝6.8Hz,3H),1.28(s,9H)；¹³C NMR(101MHz,Chloroform-d)153.9,151.1,132.4,114.6,112.6,112.4,59.7,56.0,55.9,54.1,24.6,24.4。

example 84

2t(R¹＝3,4-diMeO-Ph,R²＝CH₃,R³t-Bu) preparation

To a 10mL Schlenck tube, phosphine ligand L8(0.002mmol), nickel acetate tetrahydrate (0.5mg,0.002mmol) and 1t N-sulfonimide (0.4mmol) were added, the system was passed through a vacuum line, replaced with nitrogen gas 3 times, 1mL trifluoroethanol solvent was added, the autoclave was charged, after 6 times of hydrogen replacement, the initial hydrogen pressure was made 30bar, and the reaction was stirred at 50 ℃ for 24 hours. Cooling, carefully venting, opening the autoclave, removing the vial, draining the solvent, detecting the conversion by NMR, and performing column chromatography to obtain the product. The yield was 96% with an enantiomeric excess of 90%. 2t, the white solid is added into the solution,¹H NMR(400MHz,Chloroform-d)6.90–6.75(m,3H),4.72(d,J＝8.0Hz,1H),4.58(p,J＝6.8Hz,1H),3.87(s,3H),3.85(s,3H),1.54(d,J＝6.8Hz,3H),1.29(s,9H)；¹³C NMR(101MHz,Chloroform-d)149.3,148.4,136.6,118.2,111.3,109.5,59.9,56.1,54.5,25.7,24.4.

example 85

2u(R¹＝3,4-diMeO-Ph,R²＝CH₃,R³t-Bu) preparation

To a 10mL Schlenck tube, phosphine ligand L8(0.002mmol), nickel acetate tetrahydrate (0.5mg,0.002mmol) and N-sulfonimide 1u (0.4mmol) were added, the system was passed through a vacuum line, replaced with nitrogen gas 3 times, 1mL of trifluoroethanol solvent was added, the autoclave was charged, after 6 times of hydrogen replacement, the initial hydrogen pressure was made 30bar, and the reaction was stirred at 70 ℃ for 24 hours. Cooling, carefully venting, opening the autoclave, removing the vial, draining the solvent, detecting the conversion by NMR, and performing column chromatography to obtain the product. The yield was 99% and the enantiomeric excess was 95%. 2u of a white solid, wherein the white solid is,¹H NMR(400MHz,Chloroform-d)6.81(d,J＝1.2Hz,1H),6.79–6.73(m,2H),5.94(q,J＝1.2Hz,2H),4.64(d,J＝8.8Hz,1H),4.61–4.50(m,1H),1.53(d,J＝6.8Hz,3H),1.30(s,9H)；¹³C NMR(101MHz,Chloroform-d)148.1,147.0,138.0,119.5,108.6,106.8,101.3,60.0,54.5,25.9,24.4.

example 86

2v(R¹2-furyl radical, R²＝CH₃,R³t-Bu) preparation

To a 10mL Schlenck tube, phosphine ligand L8(0.002mmol), nickel acetate tetrahydrate (0.5mg,0.002mmol) and N-sulfonimide 1v (0.1mmol) were added, the system was passed through a vacuum line, replaced with nitrogen gas 3 times, 1mL of trifluoroethanol solvent was added, the autoclave was charged, after 6 times of hydrogen replacement, the initial hydrogen pressure was made 30bar, and the reaction was stirred at 50 ℃ for 24 hours. Cooling, carefully venting, opening the autoclave, removing the vial, draining the solvent, detecting the conversion by NMR, and performing column chromatography to obtain the product. The yield was 65% with an enantiomeric excess of 94%. 2v of a white solid, wherein the white solid is,¹H NMR(400MHz,Chloroform-d)7.38–7.32(m,1H),6.30(dd,J＝3.2,2.0Hz,1H),6.21(d,J＝2.8Hz,1H),4.66(dq,J＝9.2,6.8Hz,1H),4.33(d,J＝9.2Hz,1H),1.58(d,J＝6.8Hz,3H),1.37(s,9H)；¹³C NMR(101MHz,Chloroform-d)155.5,142.3,110.5,106.2,60.3,48.8,24.4,22.6.

example 87

2w(R¹2-naphthyl, R²＝CH₃,R³t-Bu) preparation

To a 10mL Schlenck tube, phosphine ligand L8(0.002mmol), nickel acetate tetrahydrate (0.5mg,0.002mmol) and N-sulfonimide 1w (0.1mmol) were added, the system was passed through a vacuum line, replaced with nitrogen gas 3 times, 1mL of trifluoroethanol solvent was added, the autoclave was charged, after 6 times of hydrogen replacement, the initial hydrogen pressure was made 30bar, and the reaction was stirred at 50 ℃ for 24 hours. Cooling, carefully venting, opening the autoclave, removing the vial, draining the solvent, detecting the conversion by NMR, and performing column chromatography to obtain the product. The yield was 94% and the enantiomeric excess was 97%. 2w of a white solid, wherein the white solid is,¹H NMR(400MHz,Chloroform-d)7.84(t,J＝8.4Hz,3H),7.75(s,1H),7.54–7.41(m,3H),4.88–4.81(m,1H),4.39(d,J＝8.4Hz,1H),1.66(d,J＝6.8Hz,3H),1.33(s,9H)；¹³C NMR(101MHz,Chloroform-d)141.2,133.6,133.0,129.0,128.2,127.9,126.6,126.3,124.7,124.4,60.1,54.9,25.9,24.5.

example 88

2x(R¹6' -methoxy-2-naphthyl, R²＝CH₃,R³t-Bu) preparation

To a 10mL Schlenck tube, phosphine ligand L8(0.002mmol), nickel acetate tetrahydrate (0.5mg,0.002mmol) and N-sulfonimide 1x (0.1mmol) were added, the system was passed through a vacuum line, replaced with nitrogen gas 3 times, 1mL of trifluoroethanol solvent was added, the autoclave was charged, after 6 times of hydrogen replacement, the initial hydrogen pressure was made 30bar, and the reaction was stirred at 50 ℃ for 24 hours. Cooling, carefully venting, opening the autoclave, removing the vial, draining the solvent, detecting the conversion by NMR, and performing column chromatography to obtain the product. The yield was 85% and the enantiomeric excess was 95%. 2x, the white solid is mixed with the solvent,¹H NMR(400MHz,Chloroform-d)7.71(dd,J＝8.4,5.2Hz,2H),7.68(s,1H),7.41(dd,J＝8.4,1.6Hz,1H),7.18–7.08(m,2H),4.86–4.72(m,2H),3.91(s,3H),1.65(d,J＝6.4Hz,3H),1.31(s,9H)；¹³C NMR(101MHz,Chloroform-d)158.0,139.0,134.1,129.7,128.9,127.8,125.0,124.6,119.4,105.8,60.0,55.6,54.8,25.9,24.4.

example 89

2y(R¹1-naphthyl, R²＝CH₃,R³t-Bu) preparation

To a 10mL Schlenck tube, phosphine ligand L8(0.002mmol), nickel acetate tetrahydrate (0.5mg,0.002mmol) and N-sulfonimide 1y (0.1mmol) were added, the system was passed through a vacuum line, replaced with nitrogen gas 3 times, 1mL of trifluoroethanol solvent was added, the autoclave was charged, after 6 times of hydrogen replacement, the initial hydrogen pressure was made 30bar, and the reaction was stirred at 50 ℃ for 24 hours. Cooling, carefully venting, opening the autoclave, removing the vial, draining the solvent, detecting the conversion by NMR, and performing column chromatography to obtain the product. The yield was 86% and the enantiomeric excess was 99.7%. 2y is a white solid, and the white solid,¹H NMR(400MHz,Chloroform-d)8.08(d,J＝8.4Hz,1H),7.89(d,J＝7.2Hz,1H),7.80(d,J＝8.0Hz,1H),7.61–7.46(m,4H),5.57–5.45(m,1H),4.79(d,J＝8.0Hz,1H),1.70(d,J＝6.8Hz,3H),1.28(s,9H)；¹³C NMR(101MHz,Chloroform-d)139.8,134.1,130.1,129.3,128.3,126.7,126.1,125.8,122.9,122.9,60.1,50.8,26.4,24.4.

example 90

2z(R¹＝Ph,R²＝Et,R³t-Bu) preparation

To a 10mL Schlenck tube, phosphine ligand L8(0.002mmol), nickel acetate tetrahydrate (0.5mg,0.002mmol) and N-sulfonimide 1z (0.4mmol) were added, the system was passed through a vacuum line, replaced with nitrogen gas 3 times, 1mL of trifluoroethanol solvent was added, the autoclave was charged, after 6 times of hydrogen replacement, the initial hydrogen pressure was made 30bar, and the reaction was stirred at 50 ℃ for 24 hours. Cooling, carefully venting, opening the autoclave, removing the vial, draining the solvent, detecting the conversion by NMR, and performing column chromatography to obtain the product. The yield was 99% and the enantiomeric excess was 80%. 2z is the white solid, and the white solid,¹H NMR(400MHz,Chloroform-d)7.34(t,J＝7.2Hz,2H),7.29–7.20(m,3H),4.68(d,J＝8.4Hz,1H),4.43–4.33(m,1H),1.84(ddq,J＝21.2,13.6,7.2Hz,2H),1.26(s,9H),0.90(t,J＝7.2Hz,3H)；¹³C NMR(101MHz,Chloroform-d)142.7,128.9,127.6,126.6,60.7,59.9,32.8,24.4,11.0.

example 91

2aa(R¹＝Ph,R²＝iPr,R³t-Bu) preparation

To a 10mL Schlenck tube, phosphine ligand L8(0.002mmol), nickel acetate tetrahydrate (0.5mg,0.002mmol) and N-sulfonimide 1aa (0.4mmol) were added, the system was passed through a vacuum line, replaced with nitrogen gas 3 times, 1mL of trifluoroethanol solvent was added, the autoclave was charged, after 6 times of hydrogen replacement, the initial hydrogen pressure was made 30bar, and the reaction was stirred at 50 ℃ for 24 hours. Cooling, carefully venting, opening the autoclave, removing the vial, draining the solvent, detecting the conversion by NMR, and performing column chromatography to obtain the product. The yield was 99% and the enantiomeric excess was 80%. 2aa of a white solid, and (b) a white solid,¹H NMR(400MHz,Chloroform-d)7.33(t,J＝7.2Hz,2H),7.28–7.23(m,1H),7.21–7.15(m,2H),4.74(s,1H),4.28–4.18(m,1H),1.95(h,J＝6.8Hz,1H),1.21(s,9H),1.01(d,J＝6.8Hz,3H),0.86(dd,J＝6.8,2.8Hz,3H)；¹³C NMR(101MHz,Chloroform-d)141.9,128.6,127.5,127.2,64.8,59.9,36.0,24.4,19.9,19.1.

example 92

2ab(R¹＝Ph,R²Is cyclopropyl, R³t-Bu) preparation

To a 10mL Schlenck tube, phosphine ligand L8(0.002mmol), nickel acetate tetrahydrate (0.5mg,0.002mmol) and N-sulfonimide 1ab (0.4mmol) were added, the system was passed through a vacuum line, replaced with nitrogen gas 3 times, 1mL of trifluoroethanol solvent was added, the autoclave was charged, after 6 times of hydrogen replacement, the initial hydrogen pressure was made 30bar, and the reaction was stirred at 50 ℃ for 24 hours. Cooling, carefully venting, opening the autoclave, removing the vial, draining the solvent, detecting the conversion by NMR, and performing column chromatography to obtain the product. The yield was 99% and the enantiomeric excess was 99.1%. 2ab of a white solid, and (c) a white solid,¹H NMR(400MHz,Chloroform-d)7.37–7.31(m,2H),7.31–7.24(m,3H),4.81(s,1H),4.00(t,J＝8.0Hz,1H),1.24(s,10H),0.66–0.58(m,1H),0.58–0.49(m,2H),0.43–0.33(m,1H)；¹³C NMR(101MHz,Chloroform-d)142.1,128.8,127.7,126.9,62.6,59.8,24.4,20.1,4.9,4.4.

example 93

2ac(R¹＝Ph,R²Is cyclopentyl, R³t-Bu) preparation

Phosphine ligand L8(0.002mmol), nickel acetate tetrahydrate (0.5mg,0.002mmol) and N-sulfonimide 1ac (0.4mmol) were added to a 10mL Schlenck tube, the system was passed through a vacuum line, replaced with nitrogen gas 3 times, 1mL of trifluoroethanol solvent was added, the autoclave was charged, after 6 times of hydrogen replacement, the initial hydrogen pressure was made 30bar, and the reaction was stirred at 70 ℃ for 24 hours. Cooling, carefully venting, opening the autoclave, removing the vial, draining the solvent, detecting the conversion by NMR, and performing column chromatography to obtain the product. The yield was 99% and the enantiomeric excess was 90%. 2ac of a white solid, and adding a white solid,¹H NMR(400MHz,Chloroform-d)7.32(t,J＝7.2Hz,2H),7.28–7.17(m,3H),4.65(d,J＝7.2Hz,1H),4.25(t,J＝8.8Hz,1H),2.20–2.09(m,1H),1.88(qd,J＝11.2,7.2Hz,1H),1.70–1.44(m,5H),1.38–1.30(m,1H),1.25–1.14(m,10H)；¹³C NMR(101MHz,Chloroform-d)143.1,128.7,127.5,127.0,63.3,59.8,48.7,30.4,25.3,25.1,24.4.

example 94

2ad(R¹，R²Connected to form 1-benzocyclopentyl radical, R³t-Bu) preparation

To a 10mL Schlenck tube, phosphine ligand L8(0.002mmol), nickel acetate tetrahydrate (0.5mg,0.002mmol) and N-sulfonimide 1ad (0.1mmol) were added, the system was passed through a vacuum line, replaced with nitrogen gas 3 times, 1mL of trifluoroethanol solvent was added, the autoclave was charged, after 6 times of hydrogen replacement, the initial hydrogen pressure was made 30bar, and the reaction was stirred at 70 ℃ for 24 hours. Cooling, carefully venting, opening the autoclave, removing the vial, draining the solvent, detecting the conversion by NMR, and performing column chromatography to obtain the product. The yield was 99% and the enantiomeric excess was 92%. 2ad of a white solid, wherein the white solid is,¹H NMR(400MHz,Chloroform-d)7.51–7.42(m,1H),7.26–7.22(m,3H),4.94(q,J＝8.0Hz,1H),4.12(d,J＝9.6Hz,1H),2.97(ddd,J＝16.0,8.8,3.2Hz,1H),2.82(dt,J＝16.0,8.4Hz,1H),2.64(dtd,J＝10.8,7.6,3.2Hz,1H),1.92(dq,J＝12.8,8.4Hz,1H),1.46(s,9H)；¹³C NMR(101MHz,Chloroform-d)143.0,128.5,127.2,125.1,124.5,60.6,60.1,36.1,30.1,24.6.

example 95

2ae(R¹，R²Are linked to form 1-benzocyclohexyl, R³t-Bu) preparation

To a 10mL Schlenck tube, phosphine ligand L8(0.002mmol), nickel acetate tetrahydrate (0.5mg,0.002mmol) and N-sulfonimide 1ae (0.1mmol) were added, the system was passed through a vacuum line, replaced with nitrogen gas 3 times, 1mL of trifluoroethanol solvent was added, the autoclave was charged, after 6 times of hydrogen replacement, the initial hydrogen pressure was made 30bar, and the reaction was stirred at 50 ℃ for 24 hours. Cooling, carefully venting, opening the autoclave, removing the vial, draining the solvent, detecting the conversion by NMR, and performing column chromatography to obtain the product. The yield was 72% and the enantiomeric excess was 97%. 2ae of white solid, namely white solid,¹H NMR(400MHz,Chloroform-d)7.60–7.53(m,1H),7.19(tt,J＝7.2,5.6Hz,2H),7.12–7.04(m,1H),4.65(dt,J＝9.2,6.0Hz,1H),4.12(d,J＝9.2Hz,1H),2.88–2.68(m,2H),2.15(ddt,J＝16.8,8.4,3.6Hz,1H),2.00–1.77(m,3H),1.44(s,9H)；¹³C NMR(101MHz,Chloroform-d)137.7,137.0,129.4,129.0,127.8,126.7,60.1,53.3,32.4,29.3,24.6,20.0.

example 96

2af(R¹，R³Connected to form benzodioxoisothiazole, R²＝CH₃) Preparation of

To a 10mL Schlenck tube, phosphine ligand L8(0.003mmol), nickel acetate (10.5mg,0.06mmol) and N-sulfonimide 1af (31.5mmol, S/C ═ 10500) were added, and the system was passed through a vacuum line, replaced with nitrogen gas 3 times, added 13mL of trifluoroethanol solvent, charged into an autoclave, replaced with hydrogen gas 6 times, then the initial hydrogen pressure was made 10bar, and the reaction was stirred at 60 ℃ for 72 hours. Cooling, carefully venting, opening the autoclave, removing the vial, draining the solvent, detecting the conversion by NMR, and performing column chromatography to obtain the product. The yield was 99% and the enantiomeric excess was 93%. 2af of a white solid, and a white solid,¹H NMR(400MHz,Chloroform-d)7.73(d,J＝7.6Hz,1H),7.60(t,J＝7.6Hz,1H),7.49(t,J＝7.6Hz,1H),7.37(d,J＝7.6Hz,1H),5.08(s,1H),4.84–4.65(m,1H),1.58(d,J＝6.8Hz,3H)；¹³C NMR(101MHz,Chloroform-d)141.8,135.3,133.3,129.2,129.2,124.0,123.9,121.2,121.1,53.4,53.4,21.4.

example 97

2ag(R¹，R³Connected to form benzodioxoisothiazole, R²Ph) preparation

To a 10mL Schlenck tube, phosphine ligand L8(0.002mmol), nickel acetate tetrahydrate (0.5mg,0.002mmol) and N-sulfonimide 1ag (0.4mmol) were added, the system was passed through a vacuum line, replaced with nitrogen gas 3 times, 1mL of trifluoroethanol solvent was added, the autoclave was charged, after 6 times of hydrogen replacement, the initial hydrogen pressure was made 1bar, and the reaction was stirred at 50 ℃ for 24 hours. Cooling, carefully venting, opening the autoclave, removing the vial, draining the solvent, detecting the conversion by NMR, and performing column chromatography to obtain the product. The yield was 99% and the enantiomeric excess was 90%. 2ag of a white solid, and the like,¹H NMR(400MHz,Chloroform-d)7.82(dd,J＝6.0,2.8Hz,1H),7.61–7.50(m,2H),7.42–7.36(m,5H),7.21–7.07(m,1H),5.73(d,J＝3.2Hz,1H),5.22(s,1H)；¹³C NMR(101MHz,Chloroform-d)139.8,138.8,134.7,133.4,129.5,129.3,129.1,127.6,125.4,121.1,61.4.

example 98

2ah(R¹，R³Connected to form benzodioxo 1,2, 3-oxathiazine, R²＝CH₃) Preparation of

To a 10mL Schlenck tube, phosphine ligand L8(0.002mmol), nickel acetate tetrahydrate (0.5mg,0.002mmol) and N-sulfonimide 1ah (0.4mmol) were added, the system was passed through a vacuum line, replaced with nitrogen gas 3 times, 1mL of trifluoroethanol solvent was added, the autoclave was charged, after 6 times of hydrogen replacement, the initial hydrogen pressure was made 1bar, and the reaction was stirred at 50 ℃ for 24 hours. Cooling, carefully venting, opening the autoclave, removing the vial, draining the solvent, detecting the conversion by NMR, and performing column chromatography to obtain the product. The yield was 99% and the enantiomeric excess was 97%. 2ah of white solid, wherein the white solid is,¹H NMR(400MHz,Chloroform-d)7.33–7.27(m,1H),7.23–7.18(m,2H),6.99–6.94(m,1H),4.89(p,J＝7.2Hz,1H),4.71(d,J＝7.2Hz,1H),1.71(d,J＝6.8Hz,3H)；¹³C NMR(101MHz,Chloroform-d)151.1,129.7,126.5,125.7,123.8,118.9,53.2,20.3.

example 99

2ai(R¹，R³Connected to form benzodioxo 1,2, 3-oxathiazine, R²Ph) preparation

Phosphine ligand L8(0.002mmol), nickel acetate tetrahydrate (0.5mg,0.002mmol) and N-sulfonimide 1ai (0.4mmol) were added to a 10mL Schlenck tube, the system was passed through a vacuum line, replaced with nitrogen gas 3 times, 1mL of trifluoroethanol solvent was added, the autoclave was charged, after 6 hydrogen replacements, the initial hydrogen pressure was made to 1bar, and the reaction was stirred at 50 ℃ for 24 hours. Cooling, carefully venting, opening the autoclave, removing the vial, draining the solvent, detecting the conversion by NMR, and performing column chromatography to obtain the product. The yield was 99% and the enantiomeric excess was 97%. 2ai, a white solid, and a white solid,¹H NMR(400MHz,Chloroform-d)7.45–7.43(m,3H),7.38–7.30(m,3H),7.16–7.01(m,2H),6.82(d,J＝8.0Hz,1H),5.90(d,J＝7.6Hz,1H),4.80(d,J＝7.6Hz,1H)；¹³C NMR(101MHz,Chloroform-d)151.7,138.1,130.0,129.8,129.7,129.1,128.8,125.5,122.2,119.1,62.2.

example 100

2aj(R¹，R³Connected to form benzo dioxo 1,2, 6-azathiazine, R²＝CH₃) Preparation of

To a 10mL Schlenck tube, phosphine ligand L8(0.002mmol), nickel acetate tetrahydrate (0.5mg,0.002mmol) and N-sulfonimide 1aj (0.4mmol) were added, the system was passed through a vacuum line, replaced with nitrogen gas 3 times, 1mL of trifluoroethanol solvent was added, the autoclave was charged, after 6 times of hydrogen replacement, the initial hydrogen pressure was made 1bar, and the reaction was stirred at 50 ℃ for 24 hours. Cooling, carefully venting, opening the autoclave, removing the vial, draining the solvent, detecting the conversion by NMR, and performing column chromatography to obtain the product. The yield was 99% and the enantiomeric excess was 95%. 2aj of a white solid, and a white solid,¹H NMR(400MHz,Chloroform-d)7.19–7.14(m,2H),7.08(s,1H),7.06–6.99(m,1H),6.67(d,J＝8.0Hz,1H),4.82–4.68(m,1H),4.42(d,J＝10.4Hz,1H),1.64(d,J＝6.8Hz,3H)；¹³C NMR(101MHz,Chloroform-d)137.6,128.9,126.1,124.8,123.6,118.4,53.5,19.7.

example 101

2ak(R¹，R³Connected to form benzo dioxo 1,2, 6-azathiazine, R²Ph) preparation

To a 10mL Schlenck tube, phosphine ligand L8(0.002mmol), nickel acetate tetrahydrate (0.5mg,0.002mmol) and N-sulfonimide 1ak (0.4mmol) were added, the system was passed through a vacuum line, replaced with nitrogen gas 3 times, 1mL of trifluoroethanol solvent was added, the autoclave was charged, after 6 times of hydrogen replacement, the initial hydrogen pressure was made 1bar, and the reaction was stirred at 50 ℃ for 24 hours. Cooling, carefully venting, opening the autoclave, removing the vial, draining the solvent, detecting the conversion by NMR, and performing column chromatography to obtain the product. The yield was 99% and the enantiomeric excess was 96%. 2ak is a white solid, and the solid,¹H NMR(400MHz,Chloroform-d)7.41–7.39(m,3H),7.32(dd,J＝6.8,2.8Hz,2H),7.20(t,J＝7.6Hz,1H),7.06(s,1H),6.92(t,J＝7.6Hz,1H),6.76(d,J＝8.0Hz,1H),6.71(d,J＝8.0Hz,1H),5.83(d,J＝10.0Hz,1H),4.67(d,J＝10.0Hz,1H)；¹³C NMR(101MHz,Chloroform-d)138.8,138.0,129.5,129.3,129.1,129.0,128.8,123.6,123.3,118.9,63.0.

the foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes or modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention. The embodiments and features of the embodiments of the present application may be combined with each other arbitrarily without conflict.

Claims (6)

1. A method for preparing chiral amine by asymmetric nickel catalytic hydrogenation of N-sulfimide, which is characterized by comprising the following steps:

hydrogenating N-sulfimide represented by a general formula (1) into chiral amine compound represented by a general formula (2) under the catalysis of a chiral catalyst of nickel in a solvent under certain hydrogen pressure and temperature;

wherein R is¹An aryl group having or not having a substituent, or an alkyl group having 1 to 8 carbon atoms having or not having a substituent;

R²an aryl group having or not having a substituent, or an alkyl group having 1 to 8 carbon atoms having or not having a substituent;

R³an aryl group having or not having a substituent, an alkyl group having 1 to 8 carbon atoms having or not having a substituent, an aryloxy group having 4 to 8 carbon atoms having or not having a substituent, or an arylamine group having 4 to 8 carbon atoms having or not having a substituent;

or in the general formulae (1) and (2), the R¹、R²And R³Can be respectively connected to form a ring shape;

the molar ratio of the chiral catalyst of nickel to the N-sulfimide represented by the general formula (1) is 1: 20-100000; the hydrogenation time is 1-72 hours;

the chiral catalyst of nickel is formed by complexing nickel salt with different anions and a chiral ligand;

the chiral ligand refers to any one ligand selected from L1-L17, and the structural formulas of the ligands L1-L17 are shown as follows:

wherein Ar is selected from C₆H₅、4-CH₃OC₆H₄、4-CF₃C₆H₄Or 3,5-di-tBu-4-MeOC₆H₂，n＝1-10。

2. The method for preparing chiral amine by asymmetric nickel catalytic hydrogenation of N-sulfonimide according to claim 1, wherein the nickel salt with different anions is nickel salt with anion of any one of chloride, bromide, acetate, trifluoroacetate, trifluoromethanesulfonate, sulfate and perchlorate.

3. The method for preparing chiral amine by asymmetric nickel catalytic hydrogenation of N-sulfimide according to claim 1, wherein the solvent is one or more of a non-polar solvent and a polar solvent.

4. The method for preparing chiral amine by asymmetric nickel catalytic hydrogenation of N-sulfonimide according to claim 3, wherein the solvent is at least one of toluene, diethyl ether, tetrahydrofuran, dichloromethane, 1, 2-dichloroethane, DMF, acetone, acetonitrile, methanol, ethanol, isopropanol, and trifluoroethanol.

5. The method for preparing chiral amine by asymmetric nickel catalytic hydrogenation of N-sulfimide according to claim 1, wherein in the general formulas (1) and (2), R¹、R²、R³Each represents a group selected from methyl, ethyl, isopropyl, n-butyl, cyclohexyl, 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-piperonyl phenyl, 2, 4-dimethylphenyl, 2, 4-dimethoxyphenyl, 2-furyl or a five-membered alicyclic group.

6. The method for preparing chiral amine by asymmetric nickel catalytic hydrogenation N-sulfimide according to claim 1, wherein the hydrogen pressure is 1-80 bar; the temperature is-78-80 ℃.