Axially chiral biaryl bisphosphine ligands, methods of making and using the same

Abstract

The application provides a kind of axially chiral biaryl bisphosphine ligand, with structure shown in formula I.The chiral ligand can be combined with transition metal to form chiral catalyst, and shows excellent catalytic performance; the above-mentioned ligand provided by the application has simple synthesis route, and two kinds of chiral ligands can be obtained respectively, and corresponding racemate, levorotatory body and dextrorotatory body can also be obtained; raw materials are easy to obtain, and corresponding ligand library can be conveniently established for high-throughput screening of many phosphine or nitrogen involved asymmetric catalytic reactions, so as to obtain excellent new ligands suitable for certain asymmetric catalytic reactions; the nitrogen atom contained in the bisphosphine ligand skeleton can be coordinated with metal catalyst, and can also act as internal base for certain reactions, and is expected to be applied to certain catalytic reactions requiring addition of alkali to promote.

Description

Technical Field

[0001] This invention relates to the field of organic chemistry, and in particular to a class of axially chiral biaromatic bisphosphine ligands, their preparation methods, and applications. Background Technology

[0002] Asymmetric catalytic synthesis is a current hot topic in organic synthetic chemistry research. Chiral ligands that complex with the central metal atom of a coordination catalyst have a significant impact on regulating the activity of asymmetric catalytic reactions, controlling reaction yields, optimizing product selectivity, and ensuring the optical purity of products. Currently, the organic chemistry community has made great achievements in the research of asymmetric catalytic reactions and the development of ligands, with the discovery and utilization of several highly efficient and high-quality C2-axis chiral ligands being an important component. Using transition metal catalytic systems constructed with C2-symmetric bisphosphine ligands such as BINAP and DuPHOS, chemists have achieved a series of asymmetric hydrogenation, hydroamination, and carbonylation reactions with both high activity and high enantioselectivity. Some of these reactions have been industrialized, enabling the commercial synthesis of many important drugs and natural products. However, despite our extensive and powerful ligand pool, the activity and enantioselectivity of many reactions remain less than ideal. Therefore, the design and development of high-performance chiral ligands remains, and will continue to be, a task and a hot topic in the field of asymmetric catalytic synthesis. Summary of the Invention

[0003] In view of this, the technical problem to be solved by the present invention is to provide a class of axially chiral biaromatic bisphosphine ligands, their preparation methods and applications, wherein the prepared axially chiral biaromatic bisphosphine ligands exhibit excellent catalytic performance in transition metal-catalyzed asymmetric reactions.

[0004] This invention provides a class of axially chiral biaromatic bisphosphine ligands having the structure shown in Formula I:

[0005]

[0006] Among them, R 1 R 2 R 3 R 4 R 9 R 10 R 11 R 12 The following groups, each independently selected from hydrogen, halogen, substituted or unsubstituted, are C1 to C2. 30 Alkyl groups, C1-C 30 alkoxy groups, C3-C 30 cycloalkyl or C6-C 30 aryl; R 3 and R 4 Or R 9 and R10 It can be connected as an alicyclic or aromatic ring;

[0007] R 5 R 6 R 7 R 8 Each of the following groups, individually selected from substituted or unsubstituted groups: C1 to C2 30 Alkyl groups, C3-C 30 cycloalkyl, C6-C 30 aryl or C4~C 30 heteroaryl groups;

[0008] The substitution mentioned therein is substitution by one or more of the following substituents: halogen, C1-C2. 30 Alkyl groups, C1-C 30 Halogenated alkyl groups, C1-C 30 alkoxy groups, C3-C 30 cycloalkyl, C6-C 30 aryl or C4~C 30 heteroaryl groups;

[0009] Dashed lines indicate single or double bonds.

[0010] Optionally, the R 1 R 2 R 3 R 4 R 9 R 10 R 11 R 12 The following groups, each independently selected from hydrogen, halogen, substituted or unsubstituted, are: C1-C6 alkyl, C1-C6 alkoxy, C3-C6 cycloalkyl, or C6-C6 alkyl. 12 aryl; R 3 and R 4 Or R 9 and R 10 It can be connected as a C5-C6 alicyclic ring or a C6-C1 alicyclic ring. 12 Aromatic ring.

[0011] Optionally, the R 1 R 2 R 3 R 4 R 9 R 10 R 11 R 12 All are H.

[0012] Optionally, the R 5 R 6 R 7 R 8Each group is independently selected from the following substituted or unsubstituted groups: C1-C6 alkyl groups, C3-C6 cycloalkyl groups, C6-C6 cycloalkyl groups, and C6-C6 cycloalkyl groups. 12 aryl or C4~C 12 Mixed aromatic compounds.

[0013] Optionally, the R 5 R 6 R 7 R 8 The following groups, individually selected from substituted or unsubstituted groups, are: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopentyl, cyclohexyl, phenyl, and naphthyl.

[0014] Optionally, the above substitution is performed by one or more of the following substituents: halogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C3-C6 cycloalkyl, C6-C6... 12 aryl or C4~C 12 Mixed aromatic compounds.

[0015] Optionally, the above substitution is performed by one or more of the following substituents: halogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, methoxy, ethoxy, phenyl.

[0016] In Formula I, dashed lines represent single or double bonds, meaning that the axially chiral biaromatic bisphosphine ligand has the structure shown in Formula I-a or Formula I-b:

[0017]

[0018] The chiral configuration of the aforementioned axially chiral biaromatic bisphosphine ligand can be either S-configuration or R-configuration. Based on this, the axially chiral biaromatic bisphosphine ligand has any one of the structures of formula (S)-1, (S)-2, (R)-1, and (R)-2:

[0019]

[0020] Optionally, the axially chiral biaromatic bisphosphine ligand has any of the following structures:

[0021]

[0022]

[0023] The specific compounds mentioned above can also be in the R configuration.

[0024] This invention provides a method for preparing the above-mentioned axially chiral biaromatic bisphosphine ligand.

[0025] Optionally, when the R 5 R 6 R 7R 8 When the ligand is aryl or heteroaryl, the preparation method of the axially chiral biaryl bisphosphine ligand includes the following steps:

[0026]

[0027] Starting with binaphthyldiamine, partial hydrogenation under palladium catalysis yielded 8-H-binaphthylamine;

[0028] 8-H-binaphthylamine and bromosuccinimide are mixed and brominated at the 3,3' position to give bromobinaphthyldiamine;

[0029] brominated naphthyldiamine undergoes Suzuki coupling with ortho-ester boric acid under palladium catalysis and simultaneously intramolecular esterification to yield an amide structure;

[0030] The above amide structure was dehydrated under the action of phosphorus oxychloride to obtain a chlorinated intermediate;

[0031] The above-mentioned chlorinated intermediate was subjected to a substitution reaction with a phosphine nucleophile to obtain an axially chiral bisphosphine ligand.

[0032] Similarly, the axially chiral biaryl bisphosphine ligand (R)-1 can be obtained; this ligand is axially chiral, so there are levorotatory bisphosphine ligands and dextrorotatory bisphosphine ligands. The racemic bisphosphine ligand can be obtained by mixing the two enantiomers in equal amounts or by starting from racemic binaphthyldiamine.

[0033] In the above route, the synthesized material 7 is used as the starting material to obtain the axially chiral biaromatic bisphosphine ligand (S)-2 according to the following synthetic route:

[0034]

[0035] Using compound 7 synthesized via the above route as the starting material, compound 7 is oxidized under the action of DDQ to obtain compound 10; compound 10 is dehydrated under the action of phosphorus oxychloride to obtain a chlorinated intermediate; the above chlorinated intermediate is subjected to a substitution reaction with a phosphine nucleophile to obtain an axially chiral bisphosphine ligand.

[0036] Similarly, the axially chiral biaryl bisphosphine ligand (R)-2 can be obtained; this ligand is axially chiral, so there are levorotatory and dextrorotatory bisphosphine ligands. The racemic bisphosphine ligand can be obtained by mixing the two enantiomers in equal amounts or by starting from racemic binaphthyldiamine.

[0037] When R 5 R 6 R 7 R 8 When the alkyl or cycloalkyl group is used, in the above route, the synthesized 8 or 11 is used as the starting material, and M is K / Na / Li. The axially chiral biaromatic bisphosphine ligands (S)-1 and (S)-2 are obtained according to the following synthetic route:

[0038]

[0039] Using compound 8 or compound 11 as a starting material, react with a phosphoborane complex to obtain a chlorobiaromatic intermediate;

[0040] The above-mentioned chlorobiaryl intermediate was subjected to deborane treatment in the presence of triethylenediamine (DABCO) to obtain axially chiral biaryl bisphosphine ligands;

[0041] M is Na, K, or Li.

[0042] Similarly, axially chiral biaromatic bisphosphine ligands (R)-1 and (R)-2 can be obtained; racemic bisphosphine ligands can be obtained by mixing equal amounts of the two enantiomers or by starting from racemic binaphthyldiamine.

[0043] The axially chiral biaryl bisphosphine ligands prepared by this invention can be used as reaction ligands in transition metal-catalyzed asymmetric hydrogenation, hydroamylation, carbamate, and carbonylation reactions.

[0044] The transition metals include, but are not limited to, one or more of the following: rhodium di(1,5-cyclooctadiene)tetrafluoroborate ([Rh(COD)2]BF4), ruthenium trichloride, dodecyltriruthenium dodecylcarbonyl, p-methylisopropylbenzene ruthenium(II) dichloride dimer, (1,5-cyclooctadiene)tetrafluoroborate, palladium chloride, palladium on carbon, tetra-triphenylphosphine palladium, bis-triphenylphosphine palladium dichloride, allyl palladium chloride, palladium acetate, diacetonitrile palladium chloride, and palladium trifluoroacetate.

[0045] In the above-mentioned asymmetric hydrogenation, hydroamylation, carbamate, and carbonylation reactions, the amount of the axially chiral biaromatic bisphosphine ligand added is preferably 1% to 3% of the molar amount of the reactants, more preferably 2.2%; the amount of the transition metal catalyst added is preferably 0.1% to 3% of the molar amount of the reactants, more preferably 1%.

[0046] Compared with existing technologies, this invention provides a class of axially chiral biaromatic bisphosphine ligands with the structure shown in Formula I. This chiral ligand can construct chiral catalysts with transition metals, exhibiting excellent catalytic performance. The synthetic route of the ligands provided by this invention is simple, allowing for the separate acquisition of two chiral ligands, as well as corresponding racemic, levorotatory, and dextrorotatory forms. The raw materials are readily available, facilitating the establishment of corresponding ligand libraries for high-throughput screening of many asymmetric catalytic reactions involving phosphine or nitrogen, thereby obtaining excellent novel ligands suitable for certain asymmetric catalytic reactions. The nitrogen atom in the bisphosphine ligand skeleton can both coordinate with metal catalysts and act as an internal base in certain reactions, showing promise for applications in catalytic reactions requiring base promotion. Attached Figure Description

[0047] Figure 1This is a single-crystal X-ray characterization image of the chiral ligand (S)-1a obtained in Example 7 of the present invention. Detailed Implementation

[0048] To further illustrate the present invention, the following detailed description of the axially chiral biaromatic bisphosphine ligands, their preparation methods, and applications provided by the present invention is provided in conjunction with embodiments.

[0049] Example 1

[0050] Synthesis of (S)-4:

[0051]

[0052] (S)-3 (5.4 g), Pd / C (2.8 g), and ethyl acetate (65 mL) were added to a 100 mL round-bottom flask. The reaction flask was then placed in an autoclave, and the mixture was purged with H2 (10 atm) five times, followed by H2 (50 atm). The autoclave was placed in a heating mantle at 100 °C and reacted with vigorous stirring for 8 hours until the hydrogen pressure in the autoclave no longer decreased. The reaction solution was concentrated and filtered through a silica gel column to obtain (S)-4, 4.7 g, yield: 85%; white solid.

[0053] 1 H NMR (400MHz, CDCl3) δ6.92(d,J=8.1Hz,2H),6.62(d,J=8.1Hz,2H),3.21(br,4H ),2.70-2.72(m,4H),2.24-2.31(m,2H),2.13-2.21(m,2H),1.65-1.71(m,8H).

[0054] Example 2

[0055] Synthesis of (S)-5:

[0056]

[0057] Take a clean 250 mL Schlenk flask, heat it with a hot gun to remove water, add (S)-4 (5.3 g) and ultra-dry tetrahydrofuran (100 mL) under nitrogen protection, slowly add NBS (6.8 g) at 0 °C, and react for 4 minutes while maintaining the reaction temperature below 5 °C. Then quench with saturated sodium bicarbonate and saturated sodium sulfite. Extract with ethyl acetate (50 mL x 3), combine the organic phases, wash the organic phase with saturated sodium chloride, dry with anhydrous sodium sulfate, remove the solvent under reduced pressure, and column chromatography to obtain the target product, 7.7 g, yield: 95%; white solid.

[0058] 1H NMR (400MHz, CDCl3) δ: 7.21 (s, 2H), 3.72 (s, 4H), 2.69 (t, J = 6.2Hz, 4H), 2.17-2.24 (m, 2H), 2.04-2.12 (m, 2H), 1.84-1.60 (m, 8H);

[0059] 13 C NMR (100MHz, CDCl3) δ: 23.1, 23.3, 26.9, 29.2, 107.1, 122.5, 129.1, 132.4, 135.8, 139.3;

[0060] HRMS(ESI)calcd.for C 20 H 23 Br2N2[M+H] + :449.0228.

[0061] Example 3

[0062] Synthesis of (S)-6:

[0063]

[0064] Take a clean 100 mL Schlenk flask, heat it with a hot gun to remove water, and add (S)-5 (3.1 g), 2-ethoxycarbonylphenylboronic acid (2.0 g), Pd(dppf)Cl2 (127 mg), K2CO3 (3.8 g), and anhydrous DMF (50 mL) under nitrogen atmosphere. Perform degassing and nitrogen purging three times under liquid nitrogen atmosphere. Then, place the reaction flask in a 100 °C oil bath and react vigorously for 24 hours. After the reaction is complete, cool to room temperature, extract with ethyl acetate (50 mL x 3), wash the organic phase with saturated sodium chloride, dry with anhydrous sodium sulfate, remove the solvent under reduced pressure, and column chromatography to obtain (S)-6, 3.1 g, yield: 94%; white solid.

[0065] Example 4

[0066] Synthesis of (S)-7:

[0067]

[0068] A 100 mL Schlenk flask was heated with a hot gun to remove water. Under nitrogen atmosphere, (S)-5 (2.2 g), 2-ethoxycarbonylphenylboronic acid (2.9 g), Pd(dppf)Cl2 (360 mg), K2CO3 (5.5 g), and anhydrous DMF (40 mL) were added. The reaction mixture was degassed and purged with nitrogen three times under liquid nitrogen conditions. The reaction flask was then placed in a 100°C oil bath and reacted vigorously for 24 hours. After the reaction was complete, the mixture was cooled to room temperature and extracted with ethyl acetate (50 mL x 3). The organic phase was washed with saturated sodium chloride, dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure. Column chromatography yielded (S)-7, 2.34 g, 95% yield; a white solid.

[0069] 1 H NMR(400MHz, CDCl3)δ:9.02(d,J=1.8Hz,2H),8.64(d,J=8.3Hz,2H),8.48–8.29(m,2H),7.88(d,J=7.8Hz,2H),7.79(ddd,J =8.4,7.0,1.4Hz,2H),7.51-7.63(m,2H),3.18(q,J=6.6Hz,4H),2.18-2.50(m,4H),1.80-1.98(m,4H),1.56-1.78(m,4H);

[0070] 13 C NMR (100MHz, CDCl3) δ: 23.1, 23.3, 28.1, 31.0, 121.6, 121.9, 122.0, 126.1, 126.7, 128.6, 130.5, 132.8, 137.0, 137.1, 138.7, 141.6, 152.4;

[0071] HRMS(ESI)calcd.for C 34 H 29 N₂O₂[M+H]: 497.2229.

[0072] Example 5

[0073] Synthesis of (S)-7:

[0074]

[0075] A 100 mL Schlenk flask was heated with a hot gun to remove water. Under nitrogen atmosphere, (S)-6 (2.4 g), 2-ethoxycarbonylphenylboronic acid (1.5 g), Pd(dppf)Cl2 (182 mg), K2CO3 (2.8 g), and anhydrous DMF (40 mL) were added. The reaction mixture was degassed and purged with nitrogen three times under liquid nitrogen conditions. The reaction flask was then placed in a 100°C oil bath and reacted with vigorous stirring for 24 hours. After the reaction was complete, the mixture was cooled to room temperature and extracted with ethyl acetate (50 mL x 3). The organic phase was washed with saturated sodium chloride, dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure. Column chromatography yielded (S)-7, 2.3 g, 95% yield; a white solid.

[0076] Example 6

[0077] Synthesis of (S)-8:

[0078]

[0079] Take a clean 100mL Schlenk flask, heat it with a hot gun to remove water, add (S)-7 (0.75g) and POCl3 (15mL) under nitrogen protection, then place the reaction flask at 100℃ for 24 hours. After the reaction is complete, return it to room temperature, slowly add the reaction system dropwise to ice water, adjust the alkalinity to 28% ammonia water, dissolve the filter cake in dichloromethane and wash it with water, collect the organic phase, remove the solvent under reduced pressure to obtain the target product (S)-8, 0.73g, yield: 91%; brown solid.

[0080] 1 H NMR(400MHz, CD2Cl2)δ:8.69(d,J=8.3Hz,1H),8.43(s,1H),8.34(dd,J=8.2,1.2Hz,1H),7.89(ddd,J=8.3,7.0,1.3Hz,1H),7 .70(t,J=7.7Hz,1H),3.20(qt,J=16.6,6.4Hz,2H),2.13-2.52(m,2H),1.83-1.97(m,2H),1.71(tdd,J=13.1,9.6,5.9Hz,2H);

[0081] 13 C NMR (100MHz, CD2Cl2) δ: 23.2, 23.4, 28.4, 31.1, 121.9, 122.3, 122.7, 125.0, 127.7, 128.0, 131.8, 135.1, 137.5, 138.2, 138.7, 140.7, 150.0;

[0082] HRMS(ESI)calcd.for C 34H 27 Cl2N2[M+H]: 533.1551.

[0083] Example 7

[0084] Synthesis of (S)-1a:

[0085]

[0086] Take a clean 100 mL Schlenk flask, heat it with a hot gun to remove water, cool it to room temperature, add sodium diphenylphosphine (3.0 mmol) and anhydrous tetrahydrofuran (10 mL) under a nitrogen atmosphere, and cool it to -78 °C. After the system has cooled, slowly add chloro-biaryl hydrocarbon (S)-8 (532 mg, 1.0 mmol) dissolved in anhydrous tetrahydrofuran (10 mL) with rapid stirring, then continue stirring and allow it to return to room temperature naturally, and continue the reaction for 8 hours. After the reaction is complete, column chromatography yields the target product (petroleum ether / ethyl acetate: 200:1-50:1) (S)-1a, 574 mg, yield: 69%; white solid.

[0087] 1 H NMR (400MHz, CDCl3) δ8.68(m,4H),8.17(s,2H),7.79(t,J=7.6Hz,2H),7.54(t,J=7.6Hz,2H),7.06-7.14(m,6H),6.93-6.97(m,4H),6 .78-6.82(m,4H),6.66-6.70(m,2H),6.54-6.58(m,4H),2.94-3.08(m,4H),1.94-2.11(m,4H),1.55-1.74(m,6H),1.43-1.48(m,2H);

[0088] 13 C NMR (100MHz, CDCl3) δ: 23.1, 23.2, 27.9, 31.0, 120.8, 121.1, 122.1, 126.3, 127.3, 127.4, 127.7, 127.8, 127.9, 127.9, 128.0, 128. 6,128.9,129.9,132.2,132.2,133.6,133.8,134.6,134.8,135.8,135.8,135.9,136.5,136.9,139.2,141.1,141.2,161.5,161.5;

[0089] 31 P NMR (100MHz, CDCl3) δ -9.74;

[0090] HRMS(ESI)calcd.for C 58 H 47 N2P2[M+H]: 833.3214.

[0091] [α] D 20 = -130.9 (CH2Cl2, c 1.04).

[0092] Example 8

[0093] Synthesis of (S)-1a:

[0094]

[0095] Take a clean 100 mL Schlenk flask, heat it with a hot gun to remove water, cool it to room temperature, add lithium diphenylphosphine (3.0 mmol) and anhydrous tetrahydrofuran (10 mL) under a nitrogen atmosphere, and cool it to -78 °C. After the system has cooled, slowly add chloro-aromatic hydrocarbon (S)-8 (532 mg, 1.0 mmol) dissolved in anhydrous tetrahydrofuran (10 mL) with rapid stirring, then continue stirring and allow it to return to room temperature naturally, and continue the reaction for 8 hours. After the reaction is complete, column chromatography yields the target product (petroleum ether / ethyl acetate: 200:1-50:1) (S)-1a, 607 mg, yield: 73%; white solid.

[0096] Example 9

[0097] Synthesis of (S)-1a:

[0098]

[0099] Take a clean 100 mL Schlenk flask, heat it with a hot gun to remove water, cool it to room temperature, add potassium diphenylphosphine (3.0 mmol) and anhydrous tetrahydrofuran (10 mL) under a nitrogen atmosphere, and cool it to -78 °C. After the system has cooled, slowly add chloro-biaryl hydrocarbon (S)-8 (532 mg, 1.0 mmol) dissolved in anhydrous tetrahydrofuran (10 mL) with rapid stirring. After the addition is complete, continue stirring and allow it to return to room temperature naturally. Continue the reaction for 8 hours. After the reaction is complete, column chromatography yields the target product (petroleum ether / ethyl acetate: 200:1-50:1) (S)-1a, 541 mg, yield: 65%; white solid.

[0100] Example 10

[0101] Synthesis of (S)-1b:

[0102]

[0103] Take a clean 100 mL Schlenk flask, heat it with a hot gun to remove water, cool it to room temperature, add 3.0 mmol of lithium bis(4-methylphenyl)phosphine and 10 mL of anhydrous tetrahydrofuran under a nitrogen atmosphere, and cool it to -78 °C. After the system has cooled, slowly add 532 mg (1.0 mmol) of chloro-biaryl hydrocarbon (S)-8 dissolved in 10 mL of anhydrous tetrahydrofuran while stirring rapidly. Then continue stirring and allow it to return to room temperature naturally, and continue the reaction for 8 hours. After the reaction is complete, column chromatography yields the target product (petroleum ether / ethyl acetate: 200:1-50:1) (S)-1b, 426 mg, yield: 48%; white solid.

[0104] 1 H NMR (400MHz, CDCl3) δ8.61-8.68(m,4H),8.20(s,2H),7.74-7.78(m,2H),7.50-7.54(m,2H),6.93-6.97(m,4H),6.75-6.79(m,4H),6.69(d, J=7.1Hz,4H),6.46(d,J=7.6Hz,4H),2.97-3.05(m,2H),2.88-2.95(m,2H),2.24(s,6H),1.96-2.00(m,4H),1.94(s,6H),1.49-1.74(m,8H);

[0105] 13 C NMR(100MHz, CDCl3)δ:21.2,21.5,23.0,23.2,27.9,31.1,120.1,121.0,122.2,126.3,127.8,128.0,128.4,128.5,128.6,12 8.7,129.7,132.0,132.1,132.6,132.8,133.8,134.0,134.6,134.8,136.7,136.7,137.7,137.9,139.2,141.2,161.9,161.9;

[0106] 31 P NMR (100MHz, CDCl3) δ-11.22;

[0107] HRMS(ESI)calcd.for C 62 H 55 N2P2[M+H] + :889.3840; found:889.3835;

[0108] [α] D 20= -195.5 (CH2Cl2, c 0.19).

[0109] Example 11

[0110] (S)-1c synthesis:

[0111]

[0112] Take a clean 100 mL Schlenk flask, heat it with a hot gun to remove water, cool it to room temperature, add diarylphosphine lithium (3.0 mmol) and anhydrous tetrahydrofuran (10 mL) under a nitrogen atmosphere, and cool it to -78 °C. After the system has cooled, slowly add chloro-biaryl hydrocarbon (S)-8 (532 mg, 1.0 mmol) dissolved in anhydrous tetrahydrofuran (10 mL) with rapid stirring, then continue stirring and allow it to return to room temperature naturally, and continue the reaction for 8 hours. After the reaction is complete, column chromatography yields the target product (petroleum ether / ethyl acetate: 200:1-50:1) (S)-1c, 1.0 g, yield: 73%; white solid.

[0113] 1 H NMR (400MHz, CDCl3) δ8.50 (d, J=8.4Hz, 2H), 8.40 (dd, J1=8.2Hz, J2=4.0Hz, 2H), 8.07 (s, 2H),7.66(t,J=7.7Hz,2H),7.40(t,J=7.7Hz,2H),7.16(d,J=8.0Hz,2H),6.74(d,J=8.7H z,2H),3.61(s,6H),3.38(s,6H),2.82-2.94(m,4H),2.04-2.11(m,2H),1.69-1.75(m,2H ),1.61-1.65(m,2H),1.42-1.46(m,4H),1.26-1.32(m,4H),1.20(s,36H),0.98(s,36H);

[0114] 13 C NMR(100MHz, CDCl3)δ:22.9,23.3,28.1,29.8,30.9,31.9,32.1,35.4,35.8 ,63.8,64.3,120.5,121.0,121.9,125.9,128.1,128.3,128.5,128.7,129.4 ,130.0,130.1,132.1,132.1,132.2,132.5,133.2,133.4,136.1,137.5,138.8,141.9,141.9,142.4,142.4,143.5,143.6,159.1,160.3,162.9,163.0;

[0115] 31 P NMR (100MHz, CDCl3) δ 3.71;

[0116] HRMS(ESI)calcd.for C 94 H 119 N2O4P2[M+H]:1401.8645; found:1401.8652;

[0117] [α] D 20 = +35.4 (CH2Cl2, c 0.35).

[0118] Example 12

[0119] Synthesis of (S)-1d:

[0120]

[0121] Take a clean 100 mL Schlenk flask, heat it with a hot gun to remove water, cool it to room temperature, add 3.0 mmol of dinoxyphosphine lithium and 10 mL of anhydrous tetrahydrofuran under a nitrogen atmosphere, and cool it to -78 °C. After the system has cooled, slowly add 532 mg (1.0 mmol) of chloro-biaryl hydrocarbon (S)-8 dissolved in 10 mL of anhydrous tetrahydrofuran while stirring rapidly. Then continue stirring and allow it to return to room temperature naturally, and continue the reaction for 8 hours. After the reaction is complete, column chromatography yields the target product (petroleum ether / ethyl acetate: 200:1-50:1) (S)-1d, 0.67 g, yield: 73%; white solid.

[0122] 1 H NMR (400MHz, CDCl3) δ8.54-8.58(m,4H),7.90(d,J=11.5Hz,2H),7.83(dt,J1=8.2Hz,J2=1Hz,2H),7.67-7.70(m,3H),7.49-7.61(m,11H), 7.29-7.41(m,9H),7.11-7.15(m,2H),6.97-7.06(m,6H),6.86(d,J=9.9Hz,2H),2.50-2.58(m,2H),1.92-1.99(m,2H),1.83-1.87(m,4H);

[0123] 13C NMR (100MHz, CDCl3) δ161.4,161.3,141.0,140.9,138.6,136.54,136.5,136.0,135.7,134 .23,134.2,133.9,133.7,133.4,133.08,133.06,133.03,133.0,132.1,132.0,131.2,131 .1,130.2,130.0,129.7,128.4,128.2,128.1,128.0,127.73,127.70,127.53,127.2,127.11,127.1,126.6,126.4,126.2,125.8,125.7,122.7,120.7,120.5,30.2,27.9,23.1,22.8;

[0124] 31 P NMR (100MHz, CDCl3) δ-4.52;

[0125] HRMS(ESI)calcd.for C 74 H 55 N2P2[M+H] + :1033.3840,found:1033.3832;

[0126] [α] D 20 = -252.2 (CH2Cl2, c 0.30).

[0127] Example 13

[0128] Synthesis of (S)-1e:

[0129]

[0130] Take a clean 100 mL Schlenk flask, heat it with a hot gun to remove water, cool it to room temperature, add dicyclohexylphosphine lithium borane complex (3.0 mmol) and anhydrous tetrahydrofuran (10 mL) under a nitrogen atmosphere, and cool it to -78 °C. After the system has cooled, slowly add chloro-biaryl hydrocarbon (S)-8 (532 mg, 1.0 mmol) dissolved in anhydrous tetrahydrofuran (10 mL) with rapid stirring, then continue stirring and allow it to return to room temperature naturally, and continue the reaction for 8 hours. After the reaction is complete, column chromatography yields the target product (S)-1e-BH3 (petroleum ether / ethyl acetate: 200:1-50:1), 0.45 g, yield: 51%; white solid.

[0131] 1H NMR (400MHz, CDCl3) δ9.17(d,J=8.32Hz,2H),8.70(d,J=8.44Hz,2H),8.48(s,2H),7.83(t,J=6.54Hz,2H),7.65(d,J=7.32Hz,2H),3.25(t,J=6.26Hz 4H),2.42-2.53(m,4H),1.77-1.96(m,17H),0.83-1.31(m,21H),0.59-0.70(m,9H),0.23-0.35(m,4H),-0.51--0.48(m,2H);

[0132] 13 C NMR (100MHz, CDCl3) δ23.1,23.4,25.3,25.4,25.5,25.6,26.0,26.6,26.6,26.7,26.7,26.8,26.9,26.9,27.0,27.2,28.2,31.3,31.9,32.2, 33.7,34.0,121.1,121.8,122.4,122.4,127.0,129.4,129.7,129.9,1 30.7,132.4,132.4,137.0,138.9,139.2,140.4,140.5,153.3,153.9;

[0133] 31 P NMR (100MHz, CDCl3) δ-7.9;

[0134]

[0135] Take a clean 50 mL Schlenk flask, heat it with a hot gun to remove water, cool it to room temperature, add (S)-1e-BH3 (0.3 mmol), anhydrous tetrahydrofuran (10 mL), and DABCO (0.9 mmol) under a nitrogen atmosphere. React at 40 °C for 1 hour. After the reaction is complete, rapid column chromatography is used to obtain the target product (petroleum ether / ethyl acetate: 50:1) (S)-1e, 205 mg, yield: 80%; white solid.

[0136] 1H NMR (400MHz, CDCl3) δ8.59-8.80 (m, 4H), 8.36 (s, 2H), 7.77 (ddd, J = 8.3, 7.0, 1.3Hz, 2H), 7 .59(ddd,J=8.1,6.9,1.1Hz,2H),3.20(t,J=6.4Hz,4H),2.44(td,J=6.5,2.1Hz,4H),1.89( ddd,J=14.0,6.6,4.6Hz,2H),1.75(q,J=6.5Hz,2H),1.34-1.55(m,7H),0.98-1.04(m,3H), 0.82(d,J=6.4Hz,6H), 0.75(d,J=6.3Hz,6H), 0.43(d,J=6.6Hz,6H), 0.06(d,J=6.6Hz,6H);

[0137] 13 C NMR (100MHz, CDCl3) δ23.4,23.5,23.6,23.6,23.7,23.7,24.3,24.4,24.4,24.5,26.0,26.1,26.3,26.5,28.3,31.2,36.4,36.5,38.5, 38.6,120.6,121.2,122.3,126.2,127.3,127.5,128.7,129.0,129.7,132.0,132.0,136.7,136.7,139.4,141.1,141.1,164.2,164.4;

[0138] 31 P NMR (162MHz, CDCl3) δ-38.7;

[0139] HRMS(ESI)calcd.for C 58 H 71 N2P2[M+H] + :857.5092,found:857.5098;

[0140] [α] D 20 = -52.5 (CH2Cl2, c 0.27).

[0141] Example 14

[0142] Synthesis of (S)-1f:

[0143]

[0144] Take a clean 100 mL Schlenk flask, heat it with a hot gun to remove water, cool it to room temperature, add di-n-propylphosphine borane complex (3.0 mmol) and anhydrous tetrahydrofuran (10 mL) under a nitrogen atmosphere, and cool it to -78 °C. After the system has cooled, slowly add 1.0 mmol of chloro-aromatic hydrocarbon (S)-8 dissolved in anhydrous tetrahydrofuran (10 mL) with rapid stirring, then continue stirring and allow it to return to room temperature naturally, and continue the reaction for 8 hours. After the reaction is complete, rapid column chromatography yields the target product (petroleum ether / ethyl acetate: 200:1-50:1) (S)-1f-BH3, 485 mg, yield: 67%; white solid.

[0145] 1 H NMR (400MHz, CDCl3) δ: 8.90 (d, J = 8.24Hz, 2H), 8.72 (d, J = 8.48Hz, 2H), 8.43 (s, 2H), 7 .76-7.80(m,2H),7.57-7.61(m,2H),3.22(t,J=6.24Hz,4H),2.44(s,2H),2.34(d,J= 6.56Hz,2H),1.73-1.78(m,4H),1.42-1.48(m,4H),1.31-1.37(m,1H),1.40-1.53(m, 6H),1.15-1.28(m,8H),0.87(t,J=6.60Hz,4H),0.61-0.71(m,9H)0.14-0.18(m,6H);

[0146] 13 C NMR(100MHz, CDCl3)δ:25.3,15.5,15.9,16.0,16.0,16.0,16.4,16.4,23.2,23.3,26.7,27.0,27.3,27.7,28.3,31.2,1 21.1,121.9,122.5,127.2,127.3,127.6,128.1,130.8,132.5,132.5,137.3,138.9,139.3,140.3,140.5,153.8,154.5;

[0147] 31 P NMR (100MHz, CDCl3) δ20.4;

[0148]

[0149] Take a clean 50 mL Schlenk flask, heat it with a hot gun to remove water, cool it to room temperature, add (S)-1f-BH3 (0.27 mmol), anhydrous tetrahydrofuran (10 mL), and DABCO (3.0 eq.) under a nitrogen atmosphere. React at 40 °C for 1 hour. After the reaction is complete, rapid column chromatography is used to obtain the target product (petroleum ether / ethyl acetate: 50:1) (S)-1f, 180 mg, yield: 94%; white solid.

[0150] 1 H NMR (400MHz, CDCl3) δ8.69 (d, J=8.3Hz, 2Hz), 8.61 (dd, J1=7.5Hz, J2=5.1Hz, 2H), 8.36 (s, 2H), 7.80 ( dt,J1=8.1Hz,J2=1Hz,2H),7.61(dt,J1=7.9Hz,J2=0.7Hz,2H),3.19(t,J=6.2Hz,4H),2.35-2.49(m,4 H),1.80-1.94(m,4H),1.69-1.77(m,4H),1.42-1.48(m,2H),1.31-1.40(m,4H),1.14-1.22(m,4H),1 .05-1.10(m,2H),0.93-1.01(m,2H),0.72(t,J=7.2Hz,8H),0.56-0.65(m,2H),0.22(t,J=7.2Hz,2H);

[0151] 13 C NMR (100MHz, CDCl3) δ163.4,163.3,141.1,141.1,139.5,136.7,136.6,131.91,131.9,129.7,128.8,128.6,127.4,127.2, 126.2,122.4,121.0,120.6,31.2,28.9,28.8,28.2,28.1,28.0,23.5,23.4,19.5,19.4,19.2,19.0,16.2,16.1,15.7,15.5;

[0152] 31 P NMR (100MHz, CDCl3) δ-28.16;

[0153] HRMS(ESI)calcd.for C 46 H 55 N2P2[M+H] + :697.3840, found:697.3834;

[0154] [α] D 20 = +19.7 (CH2Cl2, c 0.31).

[0155] Example 15

[0156] Synthesis of (S)-1g:

[0157]

[0158] Take a clean 100 mL Schlenk flask, heat it with a hot gun to remove water, cool it to room temperature, add 3.0 mmol of diisopropylphosphine borane complex and 10 mL of anhydrous tetrahydrofuran under a nitrogen atmosphere, and cool it to -78 °C. After the system has cooled, slowly add 1.0 mmol of chloro-aromatic hydrocarbon (S)-8 dissolved in 10 mL of anhydrous tetrahydrofuran with rapid stirring. After the addition is complete, continue stirring and allow it to return to room temperature naturally, and continue the reaction for 8 hours. After the reaction is complete, rapid column chromatography yields the target product (petroleum ether / ethyl acetate: 200:1-50:1) (S)-1 g-BH3, 280 mg, yield: 78%; white solid.

[0159] 1 H NMR (400MHz, CDCl3)δ : 9.07(d,J=8.3Hz,2H),8.70(d,J=8.4Hz,2H),8.44(s,2H),7.84(ddd,J=8.3,7.0,1.2Hz,2H),7.66(dd d,J=8.3,7.0,1.2Hz,2H),3.23(q,J=5.6Hz,4H),2.66(dt,J=17.3,5.9Hz,2H),2.50(dt,J=17.3,6.7H z,2H),2.13-2.28(m,2H),1.94-2.04(m,2H),1.67-1.92(m,4H),1.09-1.14(m,1H),0.95(dd,J=14.8, 7.2Hz, 6H), 0.80 (dd, J=14.8, 7.0Hz, 6H), 0.67 (dd, J=15.6, 7.2Hz, 6H), -0.25 (dd, J=13.9, 7.0Hz, 6H);

[0160] 31 P NMR (100MHz, CDCl3) δ 36.9.

[0161]

[0162] Take a clean 50 mL Schlenk flask, heat it with a hot gun to remove water, cool it to room temperature, add (S)-1 g-BH3 and 10 mL of anhydrous tetrahydrofuran under a nitrogen atmosphere, add DABCO (3.0 eq.) under a nitrogen atmosphere, react at 40 °C for 1 hour, and after the reaction is complete, rapid column chromatography is used to obtain the target product (petroleum ether / ethyl acetate: 50:1) (S)-1 g, 180 mg, yield: 87%; white solid.

[0163] 1 H NMR (400MHz, CDCl3) δ8.65-8.74(m,4H),8.37(s,2H),7.74-7.78(m,2H),7.53-7 .57(m,2H),3.20(t,J=5.8Hz,4H),2.52-2.67(m,4H),1.74-1.96(m,10H),1.53-1 .57(m,2H),0.90(dd,J1=13.5Hz,J2=7.2Hz,6H),0.74(dd,J1=13.5Hz,J2=7.2Hz ,6H),0.61(dd,J1=13.5Hz,J2=7.2Hz,6H),-0.22(dd,J1=13.5Hz,J2=7.2Hz,6H);

[0164] 13 C NMR(100MHz, CDCl3)δ:18.1,18.2,19.0,19.1,19.5,19.7,19.7,19.8,22.5,22.6,23.5,23.6,23.7,28.3,31.3,120.2,1 21.1,122.0,126.0,128.3,128.6,129.6,130.4,130.7,131.9,131.9,136.5,136.9,139.8,141.2,141.3,161.4,161.6;

[0165] 31 P NMR (100MHz, CDCl3) δ1.06; HRMS (ESI)calcd.for C 46 H 55 N2P2[M+H] + :697.3840, found:697.3834;

[0166] [α] D 20 = -59.4 (CH2Cl2, c 0.16).

[0167] Example 16

[0168] Synthesis of (S)-1h:

[0169]

[0170] Take a clean 100 mL Schlenk flask, heat it with a hot gun to remove water, cool it to room temperature, add 3.0 mmol of diisobutylphosphine borane complex and 10 mL of anhydrous tetrahydrofuran under a nitrogen atmosphere, and cool it to -78 °C. After the system has cooled, slowly add 1.0 mmol of chloro-aromatic hydrocarbon (S)-8 dissolved in 10 mL of anhydrous tetrahydrofuran with rapid stirring. After the addition is complete, continue stirring, allow it to return to room temperature naturally, and continue the reaction for 8 hours. After the reaction is complete, rapid column chromatography yields the target product (petroleum ether / ethyl acetate: 200:1-50:1) (S)-1h-BH3, 218 mg, yield: 44%; white solid.

[0171] 31 P NMR (100MHz, CDCl3) δ 17.3

[0172]

[0173] Take a clean 50 mL Schlenk flask, heat it with a hot gun to remove water, cool it to room temperature, add (S)-1h-BH3 (0.26 mmol) and 10 mL of anhydrous tetrahydrofuran under a nitrogen atmosphere, add DABCO (3.0 eq.) under a nitrogen atmosphere, react at 40 °C for 1 hour, and after the reaction is complete, rapid column chromatography is used to obtain the target product (petroleum ether / ethyl acetate: 50:1) (S)-1h, 160 mg, yield: 82%; white solid.

[0174] 1 H NMR (400MHz, CDCl3) δ8.66-8.71(m,4H),8.36(s,2H),7.75-7.79(m,2H),7 .57-7.61(m,2H),3.20(J=6.1Hz,4H),2.42-2.45(m,4H),1.82-1.95(m,4H) ,1.71-1.77(m,4H),1.37-1.52(m,6H),0.98-1.10(m,6H),0.83(d,J=6.4H z, 6H), 0.76 (d, J = 6.3Hz, 6H), 0.44 (d, J = 6.6Hz, 6H), 0.07 (d, J = 6.6Hz, 6H);

[0175] 13C NMR (100MHz, CDCl3) δ164.27,164.23,141.09,141.05,139.35,136.74,136.70,132.00,131.96,129.71,128.99,128.72,127.53,127.3 0,126.21,122.28,121.16,120.65,28.28,26.46,26.13,26.00,24.50,24.41,24.37,24.28,233.73,23.67,23.63,23.58,23.55,23.42;

[0176] 31 P NMR (100MHz, CDCl3) δ-38.68;

[0177] HRMS(ESI)calcd.for C 50 H 55 N2P2[M+H]:753.4466,found:753.4476;

[0178] [α] D 20 = -23.1 (CH2Cl2, c 0.28).

[0179] Example 17

[0180] Synthesis of (S)-1i:

[0181]

[0182] Take a clean 100 mL Schlenk flask, heat it with a hot gun to remove water, cool it to room temperature, add 3.0 mmol of lithium bis(3,5-di-tert-butylphenyl)phosphine and 10 mL of anhydrous tetrahydrofuran under a nitrogen atmosphere, and cool it to -78 °C. After the system has cooled, slowly add 532 mg (1.0 mmol) of chloro-biaryl hydrocarbon (S)-8 dissolved in 10 mL of anhydrous tetrahydrofuran while stirring rapidly. Then continue stirring and allow it to return to room temperature naturally, and continue the reaction for 8 hours. After the reaction is complete, column chromatography yields the target product (petroleum ether / ethyl acetate: 200:1-50:1) (S)-1i, 566 mg, yield: 44%; white solid.

[0183] Example 18

[0184] Synthesis of (S)-1j:

[0185]

[0186] Take a clean 100 mL Schlenk flask, heat it with a hot gun to remove water, cool it to room temperature, add 3.0 mmol of bis(3,5-diphenylphenyl)phosphine lithium and 10 mL of anhydrous tetrahydrofuran under a nitrogen atmosphere, and cool it to -78 °C. After the system has cooled, slowly add 532 mg (1.0 mmol) of chloro-biaryl hydrocarbon (S)-8 dissolved in 10 mL of anhydrous tetrahydrofuran while stirring rapidly. Then continue stirring and allow it to return to room temperature naturally, and continue the reaction for 8 hours. After the reaction is complete, column chromatography yields the target product (petroleum ether / ethyl acetate: 200:1-50:1) (S)-1j, 736 mg, yield: 51%; white solid.

[0187] Example 19

[0188] Asymmetric hydrogenation of α-dehydroamino acid esters:

[0189]

[0190] Inside a glove box, 0.005 mmol of [Rh(COD)₂]BF₄ and 0.011 mmol of the chiral ligand were dissolved in an ampoule containing 1 mL of dichloromethane. After stirring at room temperature for 10 minutes, 0.5 mmol of a dehydroamino acid methyl ester solution dissolved in 1 mL of dichloromethane was added. The ampoule was then transferred to an autoclave, the valve was closed, and the glove box was removed. The autoclave was purged with hydrogen three times, and then purged with hydrogen at 10 atm. The reaction was carried out at room temperature for 12 hours. After the reaction was complete, the target product was obtained by silica gel column chromatography. The conversion rate and optical purity of the product were analyzed by GC and HPLC.

[0191] Table 1 Results of asymmetric catalysis

[0192]

[0193] The results in Table 1 show that the chiral ligands prepared in this application exhibit excellent catalytic performance in the asymmetric hydrogenation reaction of dehydroamino acid methyl esters, and the reaction achieves high yield and selectivity.

[0194] The above description of the embodiments is only for the purpose of helping to understand the method and core ideas of the present invention. It should be noted that those skilled in the art can make several improvements and modifications to the present invention without departing from the principles of the present invention, and these improvements and modifications also fall within the protection scope of the claims of the present invention.

Claims

1. A class of axially chiral biaromatic bisphosphine ligands, characterized in that, It has the structure shown in Equation I: Among them, R 1 R 2 R 3 R 4 R 9 R 10 R 11 R 12 The following groups, each independently selected from hydrogen, halogen, substituted or unsubstituted, are C1 to C2. 30 Alkyl groups, C1-C 30 alkoxy groups, C3-C 30 cycloalkyl or C6-C 30 aryl; R 5 R 6 R 7 R 8 Each of the following groups, individually selected from substituted or unsubstituted groups: C1 to C2 30 Alkyl groups, C3-C 30 cycloalkyl, C6-C 30 aryl or C4~C 30 heteroaryl groups; The substitution mentioned therein is substitution by one or more of the following substituents: halogen, C1-C2. 30 Alkyl groups, C1-C 30 Halogenated alkyl groups, C1-C 30 alkoxy groups, C3-C 30 cycloalkyl, C6-C 30 aryl or C4~C 30 heteroaryl groups; Dashed lines represent single keys.

2. The axially chiral biaromatic bisphosphine ligand according to claim 1, characterized in that, Having either of the structures (S)-1 or (R)-1:

3. The axially chiral biaromatic bisphosphine ligand according to claim 1, characterized in that, The R 1 R 2 R 3 R 4 R 9 R 10 R 11 R 12 All are H.

4. The axially chiral biaromatic bisphosphine ligand according to claim 1, characterized in that, The R 5 R 6 R 7 R 8 Each group is independently selected from the following substituted or unsubstituted groups: C1-C6 alkyl groups, C3-C6 cycloalkyl groups, C6-C6 cycloalkyl groups, and C6-C6 cycloalkyl groups. 12 aryl or C4~C 12 heteroaryl groups; The substitution mentioned therein is substitution by one or more of the following substituents: halogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C3-C6 cycloalkyl, C6-C6... 12 aryl or C4~C 12 Mixed aromatic compounds.

5. The axially chiral biaromatic bisphosphine ligand according to claim 4, characterized in that, The R 5 R 6 R 7 R 8 Each of the following groups, whether substituted or unsubstituted, is independently selected: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopentyl, cyclohexyl, phenyl, naphthyl; The substitution is achieved by one or more of the following substituents: halogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, methoxy, ethoxy, and phenyl.

6. The axially chiral biaromatic bisphosphine ligand according to claim 1, characterized in that, It has any of the following structures:

7. The method for preparing the axially chiral biaromatic bisphosphine ligand according to any one of claims 1 to 6, characterized in that, Includes the following steps: Starting with binaphthyldiamine, partial hydrogenation under palladium catalysis yielded 8-H-binaphthylamine; 8-H-binaphthylamine and bromosuccinimide are mixed and brominated at the 3,3' position to give bromobinaphthyldiamine; brominated naphthyldiamine undergoes Suzuki coupling with ortho-ester boric acid under palladium catalysis and simultaneously intramolecular esterification to yield an amide structure; The above amide structure was dehydrated under the action of phosphorus oxychloride to obtain a chlorinated intermediate; The above-mentioned chlorinated intermediate was subjected to a substitution reaction with a phosphine nucleophile to obtain an axially chiral bisphosphine ligand; Among them, R 1 R 2 R 3 R 4 R 9 R 10 R 11 R 12 The following groups, each independently selected from hydrogen, halogen, substituted or unsubstituted, are C1 to C2. 30 Alkyl groups, C1-C 30 alkoxy groups, C3-C 30 cycloalkyl or C6-C 30 aryl; R 5 R 6 R 7 R 8 Each of the following groups, individually selected from substituted or unsubstituted groups: C6 to C6 30 aryl or C4~C 30 heteroaryl groups; The substitution mentioned therein is substitution by one or more of the following substituents: halogen, C1-C2. 30 Alkyl groups, C1-C 30 Halogenated alkyl groups, C1-C 30 alkoxy groups, C3-C 30 cycloalkyl, C6-C 30 aryl or C4~C 30 Mixed aromatic compounds.

8. The method for preparing the axially chiral biaromatic bisphosphine ligand according to any one of claims 1 to 6, characterized in that, Includes the following steps: Using compound 8 as a raw material, it was reacted with a phosphoborane complex to obtain a chlorobiaromatic intermediate; The above-mentioned chlorobiaryl intermediates were subjected to deborane treatment in the presence of triethylenediamine to obtain axially chiral biaryl bisphosphine ligands; Among them, R 1 R 2 R 3 R 4 R 9 R 10 R 11 R 12 The following groups, each independently selected from hydrogen, halogen, substituted or unsubstituted, are C1 to C2. 30 Alkyl groups, C1-C 30 alkoxy groups, C3-C 30 cycloalkyl or C6-C 30 aryl; R 5 R 6 R 7 R 8 Each of the following groups, individually selected from substituted or unsubstituted groups: C1 to C2 30 Alkyl groups, C3-C 30 cycloalkyl groups; The substitution mentioned therein is substitution by one or more of the following substituents: halogen, C1-C2. 30 Alkyl groups, C1-C 30 Halogenated alkyl groups, C1-C 30 alkoxy groups, C3-C 30 cycloalkyl, C6-C 30 aryl or C4~C 30 heteroaryl groups; M is Na, K, or Li.

9. The application of the axially chiral biaromatic bisphosphine ligand according to any one of claims 1 to 6 in transition metal-catalyzed asymmetric hydrogenation, hydroamylation, carbamate, and carbonylation reactions.

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