Chiral silicospirophosphine-oxazoline ligands, their ionic iridium complexes, their preparation methods and applications

Abstract

This invention belongs to the field of chemical synthesis technology, specifically a chiral silicospirocyclic phosphine-oxazoline compound, its ionic iridium complex, its preparation method, and its applications. The structural formula of the silicospirocyclic phosphine-oxazoline compound of this invention is shown below. It is a compound with wide applications, and its ionic iridium complex can be used for the catalytic hydrogenation of olefins, possessing one or more of the following advantages: high catalytic activity, a larger bite angle, and catalyst stability in air.

Description

Technical Field

[0001] This invention belongs to the field of chiral chemical synthesis technology, specifically relating to chiral silicospirocyclic phosphine-oxazoline compounds, their ionic iridium complexes, their preparation methods, and applications. Background Technology

[0002] As scientific research deepens, people have gradually realized that many phenomena in nature, especially life phenomena, are closely related to chirality. Since the basic elements of life, proteins and DNA, are chiral, when chiral drugs, chiral pesticides, etc., act on organisms, the two enantiomers often exhibit different, even opposite, biological activities. Studying chiral phenomena and developing chiral technologies requires, first and foremost, chiral compounds with single isomers. However, the types of single-isomer chiral compounds available in nature are very limited, and traditional synthetic methods can only yield racemic versions of these chiral compounds. Therefore, developing new asymmetric synthetic methods has become a new challenge for organic chemists, prompting the rapid development of asymmetric synthesis. Because asymmetric catalysis plays an important role in life sciences, materials science, medicine, pesticides, fragrances, and food additives, asymmetric catalytic synthesis has become a hot topic in the field of current organic synthetic chemistry research (Ohkuma, T.; Kitamura, M.; Noyori, R. Catalytic Asymmetric Synthesis, Wiley, New York, 2000). The integration of asymmetric synthesis research and industrialization is very close. Many new and efficient asymmetric synthesis methods are quickly applied to the industrial production of chiral compounds once discovered (Blaser, H.-U. Schmidt, E. Eds. Asymmetric Catalysis on Industrial Scale: Challenges, Approaches and Solutions. Wiley-VCH: Weinheim, Germany, 2004.). Asymmetric catalytic hydrogenation is the most economical, cleanest, and most efficient asymmetric synthesis method. In the 1970s, Knowles et al. used asymmetric hydrogenation to achieve the industrial synthesis of the chiral drug L-DOPA, pioneering the industrial application of chiral synthesis. Noyori developed the chiral bisphosphine ligand BINAP and its transition metal catalyst, realizing various types of asymmetric catalytic hydrogenation reactions and applying them to the industrial synthesis of various chiral drugs. These two chemists were awarded the 2001 Nobel Prize in Chemistry for their outstanding contributions to the field of asymmetric catalytic hydrogenation (De Vries, J. G. Elsevier, C. J. Eds. Handbook of Homogeneous Hydrogenation. Wiley-VCH: Weinheim, Germany, 2007.). While many chiral ligands and catalysts have been reported in the field of asymmetric catalytic hydrogenation, truly efficient chiral ligands and catalysts are still rare, and many important hydrogenation reactions cannot achieve efficient chiral induction. These problems directly affect the practical application of asymmetric catalytic hydrogenation.

[0003] Chiral ligands and catalysts are the source of asymmetric induction. The key to developing highly efficient and selective asymmetric catalytic hydrogenation reactions lies in the design and synthesis of corresponding chiral ligands and catalysts. Although many ligands and catalysts for asymmetric catalytic hydrogenation have been developed, they often suffer from problems such as poor stability, narrow substrate applicability, low activity, and harsh reaction conditions. Currently, the catalytic hydrogenation of many substrates remains unsolved; therefore, the development of new chiral ligands remains of significant research value. The chiral spirocyclic phosphine-oxazolin ligand developed by Professor Zhou Qilin's research group, with its ionic iridium complex catalyst Ir-(Sa,S)-DTB-SIPHOX, has successfully achieved asymmetric catalytic hydrogenation of various α,β-unsaturated carboxylic acids, including α-alkylcinnamic acid, cis-acrylic acid homologues, and α-aryl / alkoxycinnamic acid. Professor Burgess also specifically pointed out in an article that "chiral spirocyclic phosphine-nitrogen ligand iridium catalysts have shown the highest enantioselectivity to date in the hydrogenation of carboxylic acids" (Khumsubdee, S., Burgess, K. Comparison of Asymmetric Hydrogenations of Unsaturated-Carboxylic Acids and Esters. ACS Catal. 2013, 3, 237.). Recently, the renowned pharmaceutical company Roche used this asymmetric hydrogenation reaction to synthesize Aligitazar, a novel chiral drug for treating type II diabetes (Hoffmann-La Rocher Ag. Process for the preparation of propionic acid derivatives [P]. WO 2010 / 108861.). Zhejiang Jiuzhou Pharmaceutical Co., Ltd. has also successfully applied this technology to the asymmetric synthesis of the chiral drug Silodosin (Yan, P.-C. Zhang, X.-Y., Hu, X.-W. et al. First asymmetric synthesis of Silodosin through catalytic hydrogenation by using Ir-SIPHOX catalysts. Tetrahedorn Lett. 2013, 54, 449.). Given this, spirocyclic skeletons exhibit excellent reactivity and are a class of advantageous ligand skeletons. Therefore, developing new spirocyclic skeletons and expanding the ligand library is of significant research importance for promoting the development of asymmetric catalytic reactions. Summary of the Invention

[0004] The purpose of this invention is to provide a silicospirophosphine-oxazoline compound with good stability, wide substrate applicability, and high activity, its ionic iridium complex, its preparation method, and its application.

[0005] The silicospirophosphine-oxazoline compound provided by this invention has a spirosilyl dihydroindene structure, with the following specific structural formula:

[0006]

[0007] Among them, R 1 It is a C1-C6 hydrocarbon group, phenyl, substituted phenyl (the substituents on the phenyl group are C1-C6 hydrocarbon groups, alkyl groups, and haloalkyl groups, with the number of substituents being 1-5), 1-naphthyl, 2-naphthyl, or benzyl; the hydrocarbon group is methyl, ethyl, n-propyl, isopropyl, n-butyl, or tert-butyl; the alkyl group is methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, or tert-butoxy; R 2 It is a C1-C6 hydrocarbon group, phenyl group, substituted phenyl group (the substituents on the phenyl group are C1-C6 hydrocarbon groups, hydroxyl groups and haloalkyl groups, and the number of substituents is 1-5), 1-naphthyl, 2-naphthyl, benzyl; X is hexafluorophosphate, hexafluorotellurate, tetrafluoroborate, tetraphenylborate or tetra-(3,5-ditrifluoromethylphenyl)borate.

[0008] The silicospirophosphine-oxazoline compounds provided by this invention are dextrorotatory silicospirophosphine-oxazoline ligands -(R,R)-2-[(7'-diarylphosphino)-1,1'-spirosilyldihydroindene-7-]-4-substituted-4,5-dihydrooxazole or (S,R)-2-[(7'-diarylphosphino)-1,1'-spirosilyldihydroindene-7-]-4-substituted-4,5-dihydrooxazole, and levorotatory silicospirophosphine-oxazoline ligands (S,S)-2-[(7'-diarylphosphino)-1,1'-spirosilyldihydroindene-7-]-4-substituted-4,5-dihydrooxazole or (R,S)-2-[(7-diarylphosphino)-1,1'-spirosilyldihydroindene-7-]-4-substituted-4,5-dihydrooxazole.

[0009] The silicospirophosphine-oxazoline compounds have two chiral factors: axial chirality and central chirality, thus possessing four optical isomers, including two pairs of enantiomers. One pair consists of an enantiomer with a Ra configuration of the silicospirocyclic skeleton and an S configuration of the dihydrooxazole moiety, and another pair consists of an enantiomer with a Sa configuration of the silicospirocyclic skeleton and an R configuration of the dihydrooxazole moiety. The other pair consists of an enantiomer with a Sa configuration of the silicospirocyclic skeleton and an S configuration of the dihydrooxazole moiety, and another pair consists of an Ra configuration of the silicospirocyclic skeleton and an R configuration of the dihydrooxazole moiety.

[0010] This invention also provides an ionic iridium complex with silicospirophosphine-oxazoline as a ligand, the structural formula of which is:

[0011]

[0012] Therefore, the ionic iridium complexes provided by this invention actually comprise the four isomers mentioned above. These isomers have the same general chemical formula but different stereostructures and optical properties.

[0013] The method for synthesizing the silicospirophosphine-oxazoline ligand and its ionic iridium complex provided by this invention uses optically pure 1,1'-spirosilyldihydroindene-7,7'-diol as the starting material. It reacts with trifluoromethanesulfonic anhydride to form a trifluoromethanesulfonate ester, which is then coupled with a phosphonooxy compound under palladium catalysis. Trichlorosilane reduces the phosphonooxide to generate the intermediate 7-diarylphosphino-7'-trifluoromethanesulfonyloxy-1,1'-spirosilyldihydroindene. This intermediate then undergoes a palladium-catalyzed carbonylation esterification reaction. Under alkaline conditions, the ester is hydrolyzed to an acid, which is further condensed with a 2-substituted chiral aminoethanol to form an amide alcohol. This is followed by cyclization to obtain the silicospirophosphine-oxazoline ligand. Finally, it is reduced by trichlorosilane to obtain the silicospirophosphine-oxazoline ligand, which is then coordinated with metallic iridium to obtain an ionic iridium complex with the silicospirophosphine-oxazoline ligand. This complex has been used in the asymmetric hydrogenation reaction of unsaturated carboxylic acids, achieving good reaction results.

[0014] The specific steps are as follows:

[0015] (1) Using 1 to 4 equivalents of trifluoromethanesulfonic anhydride and 1 equivalent of optically pure 1,1'-spirosilydinium-7,7'-diol as raw materials, and 2 to 6 equivalents of pyridine as an acid-binding agent, the corresponding bis(trifluoromethanesulfonate) compounds are generated by reaction. The reaction temperature is 0℃ to 30℃, and the solvent is organic solvents such as dichloromethane, dichloroethane, toluene or tetrahydrofuran.

[0016] (2) The compound obtained in step (1) is reacted with 5-15 equivalents of organic amines such as diisopropylethylamine, tetramethylethylenediamine, triethylamine, n-butylamine or N,N-diethylaniline and 1-3 equivalents of diarylphosphine oxide for 1-12 hours under the catalysis of 1-10 mol% palladium acetate and 1-15 mol% 1,4-bis(diphenylphosphine)butane (dppb) to obtain a monophosphine-substituted product. The reaction solvent is an organic solvent such as dimethyl sulfoxide or N,N-dimethylformamide, and the reaction temperature is 80-150℃.

[0017] (3) The compound obtained in step (2) is reduced with a reducing agent such as trichlorosilane for 1 to 3 days in the presence of 15 to 40 equivalents of organic amines such as diisopropylethylamine, tetramethylethylenediamine, triethylamine, n-butylamine or N,N-diethylaniline to obtain a monophosphine reduction product. The reaction solvent is an organic solvent such as toluene or xylene, and the reaction temperature is 90 to 120°C.

[0018] (4) The compound obtained in step (3) is reacted with 2-15 equivalents of organic amines such as diisopropylethylamine, tetramethylethylenediamine, triethylamine, n-butylamine or N,N-diethylaniline and methanol in carbon monoxide under the catalysis of 1-10 mol% palladium acetate and 1-15 mol% 1,3-bis(diphenylphosphine)propane (dppp) for 1-24 hours to obtain a unilateral esterification product. The reaction solvent is organic solvents such as dimethyl sulfoxide or N,N-dimethylformamide, and the reaction temperature is 25℃-100℃.

[0019] (5) The esterification product obtained in step (4) is hydrolyzed in a 30-60% potassium hydroxide aqueous solution to generate an acid. The solvent used is an alcohol solvent such as methanol or ethanol. The reaction temperature is 50-100℃.

[0020] (6) The product obtained in step (5) is condensed with 2-4 equivalents of 2-substituted chiral 2-aminoethanol in the presence of 2-4 equivalents of 1-hydroxybenzotriazole (HOBt) and 3-6 equivalents of N,N-dicyclohexylcarbamide (DCC) for 1-12 hours to obtain the corresponding amide alcohol compound. The solvent used is organic solvent such as diethyl ether, tetrahydrofuran, and dioxane, and the reaction temperature is 0-50℃.

[0021] (7) The amide alcohol compound obtained in step (6) is reacted with 2-20% N,N-dimethyl-4-aminopyridine (DMAP) catalyzed, with 2-4 equivalents of triethylamine, tetramethylethylenediamine or diisopropylethylamine as acid-binding agent, and 1-1.5 equivalents of methanesulfonyl chloride, ethanesulfonyl chloride or p-toluenesulfonyl chloride as chlorinating agent, to obtain a chiral silicospirocyclic phosphono-oxazoline compound. The solvent used is dichloromethane or 1,2-dichloroethane or other organic solvents, and the reaction temperature is 0℃-50℃.

[0022] (8) The silicospirophosphine-oxazoline compound obtained in step (7) is reduced for 1 to 3 days with a reducing agent such as trichlorosilane in the presence of 15 to 40 equivalents of organic amines such as diisopropylethylamine, tetramethylethylenediamine, triethylamine, n-butylamine or N,N-diethylaniline, to obtain a chiral silicospirophosphine-oxazoline ligand. The reaction solvent is an organic solvent such as toluene or xylene, and the reaction temperature is 90 to 120°C.

[0023] Furthermore,

[0024] (9) The chiral spirophosphine-oxazoline ligand obtained in step (8) is reacted with 1-2 equivalents of a monovalent iridium compound such as [Ir(COD)Cl]2 (COD = 1,5-cyclooctadiene) and 1-3 equivalents of sodium salts with different anions for 1-20 hours to obtain the corresponding ionic iridium complexes; the solvent used is an organic solvent such as chloroform, dichloromethane or 1,2-dichloroethane, and the reaction temperature is 25℃-50℃.

[0025] The silicospirocyclic phosphine-oxazoline ligand and its corresponding ionic iridium complex prepared by this invention are important compounds with wide applications. For example, the ionic iridium complex can be used as a catalyst in solvents for the catalytic hydrogenation of prochiral compounds containing carbon-carbon double bonds.

[0026] This invention is the first to synthesize a chiral silicospirocyclic phosphine-oxazoline ligand, and uses it as a starting material to synthesize the corresponding ionic iridium complex. The iridium complex of the chiral spirocyclic phosphine-oxazoline ligand of this invention exhibits high stereoselectivity (ee value can reach 93%) when applied to the asymmetric catalytic hydrogenation of carbon-carbon double bonds, while also possessing advantages such as high reactivity and high catalytic efficiency.

[0027] Specifically, the ionic iridium complex is used as a catalyst in a solvent for the catalytic hydrogenation of prochiral compounds containing carbon-carbon double bonds. The catalytic hydrogenation process of unsaturated carboxylic acids containing carbon-carbon double bonds is described in detail below:

[0028] Under argon or nitrogen protection, the catalyst and substrate are added to the inner tube of the hydrogen reactor, followed by the addition of degassed solvent. The reactor is then tightened and purged with hydrogen 3–5 times. After the hydrogen pressure is increased to the required level, the reaction is stirred until completion. The catalyst dosage is 1%–0.05%, the hydrogen pressure is 1–50 atm, the reaction temperature is 0–60°C, and the reaction time is 1 hour–48 hours. The reaction solvent is a chloroalkanes, benzene, toluene, alcohol, or ether, such as diethyl ether or tert-butyl methyl ether.

[0029] During the reaction, one or more of the following can be added as additives: triethylamine, tetramethylethylenediamine, diisopropylamine, diisopropylethylamine, cesium carbonate, potassium carbonate, and potassium tert-butoxide.

[0030] Furthermore, the ionic iridium complex catalyst of the present invention is used for molecules with the molecular formula R 3 PhC = CR 4 The catalytic hydrogenation of unsaturated carboxylic acids of COOH exhibits good stereoselectivity, with an ee value reaching up to 93%.

[0031] The catalyst of this invention has good reactivity and can complete the conversion under normal pressure; at the same time, the iridium catalyst is stable in air and has a larger engagement angle with metals. Attached Figure Description

[0032] Figure 1 For ligand (S a Single crystal of the product after coordination complexation of ,S)-2-[(7-diphenylphosphino)-1,1'-spirosilydinium-7-]-4-benzyl-4,5-dihydrooxazole with metal [Ir(COD)Cl]2. Detailed Implementation

[0033] The present invention will be further described below through implementation examples, but these examples do not limit the scope of the invention.

[0034] Example 1: Synthesis of (S)-7,7'-bis(trifluoromethanesulfonyloxy)-1,1'-silicone dihydroindene:

[0035]

[0036] Add (S)-1,1'-spirosilyl indene-7,7'-diol (10.0 g, 39.6 mmol), pyridine (8.0 mL, 99 mmol), and 100 mL dichloromethane to a 250 mL reaction flask. Cool the flask to below 0 °C in a low-temperature magnetically stirred water bath, and add trifluoromethanesulfonic anhydride (22.3 mL, 118.8 mmol) dropwise using a constant-pressure dropping funnel. After the addition is complete, stir at room temperature for 6 hours. After the reaction is detected by thin-layer chromatography, dilute the reaction solution with 150 mL of dichloromethane, then transfer it to a separatory funnel and wash successively with 5% HCl solution, saturated saline, saturated NaHCO3 solution, and saturated saline. Finally, dry with anhydrous Na2SO4. Filter and remove the solvent by rotary evaporation, dissolve in an appropriate amount of dichloromethane, and purify by column chromatography using petroleum ether as the eluent. Solvent was removed by rotary evaporation to give 20 g of (S)-7,7'-bis(trifluoromethanesulfonyloxy)-1,1'-spirodihydroindene, a white solid, in 95% yield. mp: 76.2–77.0 °C. [α] D 25 = -75.2 (c = 0.5, CH2Cl2). 1 H NMR (400MHz, CDCl3) δ7.45(t,J=7.9Hz,2H),7.35(d,J=7.6Hz,2H),7.13(d,J=8.1Hz,2H),3.45(ddd,J=16.0,9.5, 6.1Hz,2H),3.29(ddd,J=17.4,9.9,4.1Hz,2H),1.64(ddd,J=15.7,9.6,4.2Hz,2H),1.34(dt,J=15.6,5.8Hz,2H). 13C NMR (100MHz, CDCl3) δ158.3, 154.0, 132.9, 128.1, 125.9, 118.4 (q, J = 320.2Hz), 117.0, 31.4, 9.0. 19 F NMR(376MHz,CDCl3)δ-74.11.HRMS(ESI)m / z calcd forC 18 H 14 F6NaO6S2Si,[M+Na] + =554.9797,found:554.9799.

[0037] Example 2: Synthesis of (S)-7-diphenylphosphono-7'-trimethylmethanesulfonyloxy-1,1'-spirosilyldihydroindene:

[0038]

[0039] In a 100 mL reaction flask, (S)-7,7'-bis(trifluoromethanesulfonyloxy)-1,1'-spirosilyldihydroindene (4.0 g, 7.75 mmol), diphenylphosphine oxide (3.13 g, 15.5 mmol), palladium acetate (87 mg, 0.39 mmol), 1,4-bis(diphenylphosphine)butane (dppb, 166 mg, 0.39 mmol), and 25 mL of dry DMSO were added. The mixture was magnetically stirred until thoroughly mixed. After adding N,N-diisopropylethylamine (4.1 g, 32 mmol), the mixture was heated to 100 °C and reacted for 6 hours. The mixture was cooled to room temperature, diluted with ethyl acetate, and poured into a separatory funnel. It was then washed sequentially with 5% HCl solution, saturated brine, saturated NaHCO3 solution, and saturated brine, and dried over anhydrous Na2SO4. After filtration and solvent removal via rotary evaporation, the solution was purified by silica gel column chromatography (eluent: petroleum ether / EtOAc = 4:1) to yield 3.7 g of (S)-7-diphenylphosphono-7'-trifluoromethanesulfonyloxy-1,1'-spirosilylatedindene, a white solid, in yield: 85%. mp: 163.2–165.0 °C. [α] D 25 =-90.4 (c=0.5, CH2Cl2). 1HNMR (400MHz, CDCl3) δ7.43 (qd, J=7.2, 6.1, 4.1Hz, 4H), 7.30 (dtd, J=21.8, 7.5, 3.0Hz, 4H), 7 .20–7.04(m,6H),6.97(dd,J=12.6,7.3Hz,1H),6.59(p,J=4.2Hz,1H),3.59(ddd,J=16.3,10. 4,5.1Hz,1H),3.30(dddd,J=16.1,9.9,5.7Hz,1H),3.13(dddd,J=26.9,17.1,10.0,4.3Hz,2H) ,1.82(ddd,J=14.6,10.4,3.8Hz,1H),1.36(ddd,J=15.0,9.9,4.8Hz,1H),1.22–0.97(m,2H). 13 C NMR (100MHz, CDCl3) δ158.8,157.7,157.5,153.3,138.9,138.7,138.1,137.1,133.9,132.9,132.6,132.1,132.0,131.6,131.5,131. 4,131.3,130.9,130.8,130.6,129.7,129.5,129.3,128.45,128.3,128.1,128.0,125.5,119.8,116.6,116.1,32.5,31.5,10.8,10.3. 31 P NMR (162MHz, CDCl3) δ31.4. 19 F NMR(376MHz,CDCl3)δ-74.57.HRMS(ESI)m / zcalcd for C 29 H 23 F3NaO4PSSi,[M+Na] + =607.0752,found:607.0755.

[0040] Example 3: Synthesis of (S)-7-bis(p-methoxyphenyl)phosphono-7'-trimethylmethanesulfonyloxy-1,1'-spirosilyldihydroindene:

[0041] Prepared from (S)-7,7'-bis(trifluoromethanesulfonyloxy)-1,1'-spirosilydinium and di-p-methoxyphenylphosphonite, using the same method as in Example 2. A white solid was obtained, yield: 80%, mp: 155-156℃. [α] D 25 =-92.4 (c=0.5, CH2Cl2). 1H NMR (400MHz, CDCl3) δ7.56-7.48(m,2H),7.43(d,J=7.6Hz,2H),7.25-7.21(m,2H),7.20-7.12(m,2H),7.02-6.96(m,2H),6.95-6.8 8(m,2H),6.66-6.58(m,2H),3.84(s,3H),3.71(s,3H),3.63-3.53(m,2H),3.17-3.09(m,2H),1.40-1.31(m,2H),0.96-0.87(m,2H). 13 C NMR (100MHz, CDCl3) δ161.9(d,J=2.8Hz), 161.5(d,J=2.8Hz), 156.5(d,J=13.3H z),144.0(d,J=14.1Hz),136.0(d,J=109.5Hz),134.2(d,J=11.6Hz),133.7(d,J =10.6Hz),129.4(d,J=15.6Hz),125.8(d,J=106Hz),125.3(d,J=107Hz),128.0( d, J=13.4Hz), 113.7 (d, J=12.6Hz), 113.2 (d, J=13.1Hz), 55.2, 54.9, 32.5, 11.7. 31 P NMR (162MHz, CDCl3) δ 29.5. 19 F NMR(376MHz,CDCl3)δ-75.5.HRMS(ESI)m / z calcd forC 31 H 28 F3NaO6PSSi,[M+Na] + =667.0963,found:667.0965.

[0042] Example 4: Synthesis of (S)-7-bis(p-methylphenyl)phosphono-7'-trimethylmethanesulfonyloxy-1,1'-spirosilydinium:

[0043] Prepared from (S)-7,7'-bis(trifluoromethanesulfonyloxy)-1,1'-spirosilydinium and di-p-methylphenylphosphonic acid, using the same method as in Example 2. A white solid was obtained, yield: 82%, mp: 165-166℃. [α] D 25 = -89.4 (c = 0.5, CH2Cl2). 1H NMR (400MHz, CDCl3) δ7.53-7.45(m,2H),7.43(d,J=7.6Hz,2H),7.26-7.13(m,6H),6.99(dd,J=12.4,7.6Hz,2H),6.93(dd, J=8.0,2.4Hz,2H),3.65-3.56(m,2H),3.16-3.08(m,2H),2.39(s,3H),2.27(s,3H),1.38-1.30(m,2H),0.97-0.86(m,2H). 13 C NMR (100MHz, CDCl3) δ156.69 (d, J = 13.3Hz), 143.88 (d, J = 14.5Hz), 141.51 (d, J = 2.7Hz), 141.03(d,J=2.8Hz), 135.75(d,J=108.6Hz), 132.47(d,J=10.4Hz), 132.00(d,J=9.7Hz), 131.41(d,J=58.6Hz), 130.39(d,J=60.0Hz), 129.51(d,J=15.6Hz), 129.29(d,J=3.1Hz), 128.94(d,J=12.0Hz), 128.52(d,J=12.4Hz), 128.07(d,J=13.6Hz), 32.60, 21.59, 11.78. 31 P NMR (162MHz, CDCl3) δ 30.1. 19 F NMR(376MHz,CDCl3)δ-74.3.HRMS(ESI)m / zcalcd for C 31 H 28 F3NaO4PSSi,[M+Na] + =635.1065,found:635.1063.

[0044] Example 5: Synthesis of (S)-7-bis(3,5-dimethylphenyl)phosphono-7'-trimethylmethanesulfonyloxy-1,1'-spirosilyldihydroindene:

[0045] Prepared from (S)-7,7'-bis(trifluoromethanesulfonyloxy)-1,1'-spirosilyldihydroindene and di-p-methylphenylphosphonic acid, using the same method as in Example 2. A white solid was obtained, yield: 75%, mp: 181-182℃. [α] D 25 = -80.2 (c = 0.5, CH2Cl2). 1H NMR (400MHz, CDCl3) δ7.46(d,J=7.2Hz,2H),7.31-7.26(m,4H),7.15-7.08(m,2H),6.95(s,2H),6.88(d,J=12.4 Hz,2H),3.63-3.55(m,2H),3.19-3.08(m,2H),2.32(s,6H),2.04(s,6H),1.27-1.20(m,2H),0.95-0.85(m,2H). 13 C NMR (100MHz, CDCl3) δ155.9(d,J=13.4Hz), 144.5(d,J=13.8Hz), 137.6(d,J=12.1H z),137.1(d,J=12.6Hz),135.7(d,J=107.9Hz),134.5(d,J=10.9Hz),133.5(d,J=1 2.9Hz), 132.9(d,J=2.9Hz), 132.8(d,J=2.8Hz), 130.1(d,J=10.3Hz), 129.6(d,J= 9.1Hz), 129.4 (d, J = 15.6Hz), 129.1, 128.1 (d, J = 13.5Hz), 32.4, 21.4, 21.1, 11.7. 31 P NMR (161MHz, CDCl3) δ 29.87. 19 F NMR(376MHz,CDCl3)δ-74.7.HRMS(ESI)m / z calcd for C 33 H 32 F3O4P Na SSi,[M+Na] + =663.1378,found:663.1375.

[0046] Example 6: Preparation of (S)-7-diphenylphosphino-7'-trifluoromethanesulfonyloxy-1,1'-spirodihydroindene:

[0047]

[0048] In a 100 mL reaction flask, (S)-7-diphenylphosphono-7'-trifluoromethanesulfonyloxy-1,1'-spirosilydihydroindene (1.4 g, 2.5 mmol), diisopropylethylamine (13.2 g, 102 mmol), and 50 mL of toluene were added. After cooling to 0 °C, trichlorosilane (4.0 mL, 39 mmol) was slowly added while stirring at 0 °C. The ice bath was removed, and the mixture was heated in an oil bath to 110 °C with stirring for 2 days. After cooling to room temperature, the mixture was diluted with ethyl acetate, the reaction was quenched with saturated ammonium chloride solution, filtered, the filter cake was washed with ethyl acetate, and dried over anhydrous sodium sulfate. After removing the solvent by rotary evaporation concentration, the product was purified by silica gel column chromatography (elution buffer: petroleum ether / EtOAc = 30:1) to obtain (S)-7-diphenylphosphino-7'-trifluoromethanesulfonyloxy-1,1'-spirosilyldihydroindene (0.95 g, 85%). The product was an oily substance, and solid precipitated out when left at room temperature overnight. [α] D 25 = -190.2 (c = 1.0, CH2Cl2). 1 H NMR (400MHz, CDCl3) δ7.26–7.18(m,5H),7.17–7.12(m,2H),7.10–7.03(m,3H),6.99(td, J=7.3,6.9,1.5Hz,2H),6.79(ddd,J=6.2,4.0,2.2Hz,1H),6.76–6.70(m,2H),6.66(dd,J= 6.9,2.0Hz,1H),3.50(ddd,J=16.6,9.6,6.6Hz,1H),3.32(ddd,J=16.4,9.8,6.1Hz,1H),3 .17(ddt,J=17.6,9.8,3.9Hz,2H),1.42(dtd,J=15.5,9.8,3.6Hz,2H),1.19–1.06(m,2H). 13 C NMR (100MHz, CDCl3) δ166.9,155.8,154.4,154.3,145.8,145.3,142.3,142.2,138.7,138.7,137.9,137.8,136.0,135.9,133.7,133.6,133.4 ,133.2,133.0,130.3,130.2,129.7,129.63,128.3,128.2,128.2,128. 1,127.8,127.8,127.7,126.3,50.8,32.3,32.2,32.0,10.6,10.5,9.5. 31 P NMR (161MHz, CDCl3) δ-7.23. 19F NMR(376MHz,CDCl3)δ-73.8.HRMS(ESI)m / z calcd for C 29 H 24 F3O3P Na SSi,[M+Na] + =591.0803,found:591.0805.

[0049] Example 7: Synthesis of (S)-7-bis(p-methoxyphenyl)phosphino-7'-trimethylmethanesulfonyloxy-1,1'-spirosilydinium:

[0050] Prepared from (S)-7,7'-bis(trifluoromethanesulfonyloxy)-1,1'-spirosilydinium and di-p-methoxyphenylphosphonite, using the same method as in Example 6. The product was an oily substance; upon standing at room temperature overnight, solids precipitated. Yield: 73%. [α] D 25 =-201.1 (c=1,CH2Cl2). 1 H NMR(400MHz, CDCl3) δ7.29(d,J=4.9Hz,2H),7.09(t,J=7.4Hz,2H),6.87(t,J=10.0Hz,4H), 6.64(m,6H),3.82(s,3H),3.73(s,3H),3.60(m,2H),3.23(m,2H),1.19(m,2H),1.03(m,2H). 13 C NMR (100MHz, CDCl3) δ159.6, 155.2 (d, J = 14.7Hz), 143.8, 135.0 (d, J = 21.2Hz), 134.3 (d, J = 19.3Hz), 130.3, 130.0, 130.1 ,129.8,128.7,128.6,126.3,113.9(d,J=6.7Hz),113.5(d,J=7.9Hz),55.1,54.97,32.0(d,J=8.3Hz),10.0(d,J=6.3Hz). 31 P NMR (161MHz, CDCl3) δ-8.6. 19 F NMR(376MHz,CDCl3)δ-75.3.HRMS(ESI)m / z calcd for C 31 H 28 F3NaO5PSSi,[M+Na] + =651.1014,found:651.1016.

[0051] Example 8: Synthesis of (S)-7-bis(p-methylphenyl)phosphino-7'-trimethylmethanesulfonyloxy-1,1'-spirosilydinium:

[0052] Prepared from (S)-7,7'-bis(trifluoromethanesulfonyloxy)-1,1'-spirosilydinium and di-p-methylphenylphosphonic acid, using the same method as in Example 6. The product was an oily substance; upon standing at room temperature overnight, solids precipitated. Yield: 70%. [α] D 25 = -194.2 (c = 1, CH2Cl2). 1 H NMR (400MHz, CDCl3) δ7.31-7.27(m,2H),7.14-7.09(m,2H),7.08-7.04(m,4H),6.93-6.90(m,2H),6.87(d,J=8.0Hz,2H),6. 66(t,J=8.0Hz,2H),3.64-3.56(m,2H),3.25-3.19(m,2H),2.36(s,3H),2.28(s,3H),1.21-1.14(m,2H),1.07-0.98(m,2H). 13 C NMR (100MHz, CDCl3) δ 155.2 (d, J = 15.4Hz), 146.0, 145.5, 143.1 (d, J = 8.1Hz), 137.66 (d, J = 5.Hz), 135.5 (d, J = 11.1Hz), 134.1 (d, J = 11.1Hz), 133.6 ( d,J=19.9Hz),133.0(d,J=18.1Hz),130.6,129.8,129.0(d,J=6.2Hz),128 .7(d,J=7.2Hz),126.4,31.9(d,J=8.6Hz),21.3,21.3,10.0(d,J=5.2Hz). 31 P NMR (162MHz, CDCl3) δ-8.27. 19 F NMR(376MHz,CDCl3)δ-73.8.HRMS(ESI)m / z calcd for C 31 H 28 F3NaO3PSSi,[M+Na] + =619.1116,found:619.1114.

[0053] Example 9: Synthesis of (S)-7-bis(3,5-dimethylphenyl)phosphino-7'-trimethylmethanesulfonyloxy-1,1'-spirosilyldihydroindene:

[0054] Prepared from (S)-7,7'-bis(trifluoromethanesulfonyloxy)-1,1'-spirosilydinium and di-p-methylphenylphosphonite, using the same method as in Example 6. The product was an oily substance; upon standing at room temperature overnight, solids precipitated. Yield: 60%. [α] D 25 = -155.7 (c = 0.5, CH2Cl2). 1 H NMR(400MHz, CDCl3)δ7.33(s,2H),7.09(s,2H),6.88(s,2H),6.77-6.73(m,2H),6.38-6.22 (m,4H),3.59-3.50(m,2H),3.28-3.10(m,2H),1.99(s,6H),2.22(s,6H),1.14-0.98(m,4H). 13 C NMR (100MHz, CDCl3) δ 155.1 (d, J = 16.0Hz), 146.9, 146.3, 143.3 (d, J = 8.6Hz), 139.1 (d, J = 11.9Hz), 137.5, 137.3 (d, J = 6.6Hz), 137.0 (d, J = 7. 8Hz), 131.5 (d, J = 20.5Hz), 130.8, 130.5 (d, J = 17.7Hz), 129.9, 129.8 (d, J = 62.8Hz), 126.4, 31.9 (d, J = 9.2Hz), 21.4, 21.1, 10.0 (d, J = 5.5Hz). 31 P NMR (161MHz, CDCl3) δ-6.80. 19 F NMR (376MHz, CDCl3)

[0055] δ-74.5.HRMS(ESI)m / z calcd for C 33 H 32 F3O3P Na SSi,[M+Na] + =647.1429,found:647.1425.

[0056] Example 10: Preparation of (S)-7-diphenylphosphino-7'-methoxyacyl-1,1'-spirosilyldihydroindene:

[0057]

[0058] MeOH (60 mL), DMSO (90 mL), and Et3N (24 mL), (S)-7-diphenylphosphino-7'-trifluoromethanesulfonyloxy-1,1'-spirodihydroindene (3.13 g, 5.6 mmol), Pd(OAc)2 (190 mg, 0.85 mmol), and dppp (356 mg, 0.85 mmol) were added to a 250 mL three-necked flask equipped with a three-way stopper and a reverse stopper. After stirring thoroughly, the mixture was degassed three times under a CO (1 atm) atmosphere. The system was then replaced with a CO atmosphere and heated to 70 °C using a heating module. The reaction was stirred for 6 hours, during which the system changed from orange to black. Thin-layer chromatography was used to monitor the reaction until it was complete. The solvent was removed by rotary evaporation, and the residue was redissolved in ethyl acetate. Purification was performed by silica gel column chromatography using ethyl acetate / petroleum ether (1:20) as eluent to give compound (S)-7-diphenylphosphino-7'-methoxyacyl-1,1'-spirosilyldihydroindene (2.4 g, 91%). The product was a colorless, viscous liquid that slowly solidified upon prolonged exposure to room temperature. [α] D 25 = -193.2 (c = 1.0, CH2Cl2). 1 H NMR (400MHz, CCDCl3) δ7.65(dt,J=7.5,1.1Hz,1H),7.38–7.28(m,7H),7.24–7.20(m,2H),7.17(d,J=1.2Hz,1H),7.16(d,J=1 .6Hz,1H),7.13(dt,J=7.7,1.3Hz,4H),2.60(ddd,J=7.7,5.7,1.0Hz,1H),2.50–2.38(m,3H),2.35(s,3H),1.42–1.34(m,4H). 13 C NMR (100MHz, CDCl3) δ166.5,159.1,152.6,143.9,144.9,136.9,135.7,134.0,131.2, 130.9,129.6,128.5,128.1,128.0,120.4,116.4,115.6,32.8,31.4,25.7,15.7,14.7. 31 P NMR (161MHz, CDCl3)

[0059] δ-6.80.HRMS(ESI)m / z calcd for C 30 H 27 O2PNaSSi,[M+Na] + =501.1416,found:501.1414.

[0060] Example 11: Synthesis of (S)-7-bis(p-methoxyphenyl)phosphino-7'-methoxyacyl-1,1'-spirosilyldihydroindene:

[0061] Using (S)-7,7'-bis(trifluoromethanesulfonyloxy)-1,1'-spirosilyldihydroindene as the starting material, the method was the same as in Example 10. The product was an oily substance; upon standing at room temperature overnight, solids precipitated. Yield: 60%. [α] D 25 =-200.1 (c=1,CH2Cl2). 1 H NMR (400MHz, CDCl3) δ7.55(dt,J=7.5,1.1Hz,1H),7.33(t,J=1.3Hz,2H),7.31(t,J=1.3Hz,2H),7.28–7.20(m,1H),7.20–7.18(m,2H),7.17(d,J=1 .1Hz,1H),7.1(d,J=1.6Hz,1H),6.88–6.69(m,4H),3.7(s,6H),2.5(ddd, J=7.7,5.7,1.0Hz,1H),2.45–2.38(m,3H),2.3(s,3H),1.38–1.35(m,4H). 13 C NMR (100MHz, CDCl3) δ168.5,160.2,159.1,153.6,144.9,144.8,138.9,136.3,130. 2,129.9,129.6,129.1,128.1,122.4,117.4,115.6,114.7,55.3,20.7,14.7,14.7. 31 P NMR(161MHz,CDCl3)δ-5.80.HRMS(ESI)m / z calcd forC 32 H 31 O4PNaSSi,[M+Na] + =561.1627,found:561.1625.

[0062] Example 12: Synthesis of (S)-7-bis(p-methylphenyl)phosphino-7'-methoxyacyl-1,1'-spirosilyldihydroindene:

[0063] Using (S)-7,7'-bis(trifluoromethanesulfonyloxy)-1,1'-spirosilyldihydroindene as the starting material, the method was the same as in Example 10. The product was an oily substance; upon standing at room temperature overnight, solids precipitated. Yield: 73%. [α] D 25 = -194.2 (c = 1, CH2Cl2). 1H NMR(400MHz, CDCl3)δ7.65(dt,J=7.5,1.1Hz,1H),7.33–7.30(m,1H),7.26(d ,J=1.3Hz,2H),7.24(q,J=1.3Hz,3H),7.23–7.19(m,1H),7.17(d,J=1.2Hz,1 H),7.16(t,J=1.2Hz,1H),7.11–7.05(m,4H),2.60(ddd,J=7.7,5.7,1.0Hz,1 H),2.52–2.42(m,2H),2.40(d,J=0.9Hz,6H),2.35(s,3H),1.40–1.34(m,4H). 13 C NMR (100MHz, CDCl3) δ167.5,158.1,152.6,143.9,143.9,137.9,137.7,133.9,132.8,130 .2,129.9,129.7,129.6,126.1,123.4,117.4,115.6,32.8,32.4,22.2,20.7,14.7,13.7. 31 P NMR(161MHz,CDCl3)δ-6.30.HRMS(ESI)m / z calcd for C 32 H 31 O2PNaSSi,[M+Na] + =529.1729,found:529.1725.

[0064] Example 13: Synthesis of (S)-7-bis(3,5-dimethylphenyl)phosphino-7'-methoxyacyl-1,1'-spirosilyldihydroindene:

[0065] Using (S)-7,7'-bis(trifluoromethanesulfonyloxy)-1,1'-spirosilyldihydroindene as the starting material, the method was the same as in Example 10. The product was an oily substance; upon standing at room temperature overnight, solids precipitated. Yield: 75%. [α] D 25 = -178.7 (c = 0.5, CH2Cl2). 1H NMR (400MHz, CDCl3) δ7.45(dt,J=7.5,1.1Hz,1H),7.22(dq,J=7.0,1.1Hz,1H),7.15–7.02(m,2H),7.15(d,J=1.3Hz,1H),7.01(t,J=1.2Hz,1H),6. 75(dt,J=1.6,1.0Hz,4H),6.56(t,J=1.6Hz,2H),2.54(ddd,J=7.7,5.7,1 .0Hz,1H),2.4–2.2(m,3H),2.4(s,3H),2.15(s,12H),1.33–1.12(m,4H). 13 CNMR (100MHz, CDCl3) δ168.5,159.1,153.7,144.9,144.1,140.3,138.9,136.3,130.2,130 .0,129.91,129.6,128.2,128.1,122.4,117.4,115.6,32.8,32.4,21.1,20.7,14.7,14.7. 31 P NMR(161MHz,CDCl3)δ-7.5.HRMS(ESI)m / z calcd for C 34 H 35 O2PNaSSi,[M+Na] + =557.2045,found:557.2044.

[0066] Example 14: Preparation of (S)-7-diphenylphosphino-7'-carboxyl-1,1'-spirosilyldihydroindene:

[0067]

[0068] Add (S)-7-diphenylphosphino-7'-methoxyacyl-1,1'-spirosilyldihydroindene (1.5 g, 3.25 mmol) to a 100 mL single-necked flask, and add MeOH (30 mL) while stirring to dissolve. Then, slowly add 50% KOH aqueous solution (7.5 mL). As KOH is added, a white precipitate gradually forms. The system is then purged with nitrogen and heated to 90 °C under reflux. As the temperature increases, the precipitate dissolves, and the system becomes clear and transparent. The reaction is carried out at this temperature for 3 hours, monitored by TLC, until the reaction is complete. Concentrated hydrochloric acid is carefully added dropwise to the system under an ice-salt bath until pH = 2, and a large amount of white precipitate forms. The mixture is then diluted with 50 mL of water, extracted with ethyl acetate (100 mL x 3), separated, and the organic phases are combined. Finally, the mixture is washed with saturated brine and dried over anhydrous Na₂SO₄. The filter cake was washed with ethyl acetate, the filtrate was collected, the solvent was removed by rotary evaporation, and the residue was purified by silica gel column chromatography with petroleum ether:ethyl acetate (5:1) as the eluent to give compound (S)-7-diphenylphosphino-7'-carboxyl-1,1'-spirosilyldihydroindene (1.4 g, 98%), white solid, mp: 136-137 °C. 1 H NMR (400MHz, CDCl3) δ8.20(dd,J=8.0,1.2Hz,1H),7.65(dt,J=7.5,1.1Hz,1H),7.48(dq,J=7.8,1.1Hz,1H),7.38–7.21(m,9H),7. 13(dt,J=7.7,1.3Hz,4H), 2.62(dddd,J=14.4,7.5,5.8,1.0Hz,2H), 2.42(dddd,J=21.6,7.7,5.7,1.0Hz,2H), 1.41–1.32(m,4H). 13 C NMR (100MHz, CDCl3) δ171.0,152.7,143.9,142.3,139.2,137.5,136.7,135.9,134. 6,132.2,129.5,128.8,128.0,126.8,126.4,126.0,123.4,32.8,32.0,18.7,17.6. 31 PNMR(161MHz,CDCl3)δ-11.2.HRMS(ESI)m / zcalcd for C 29 H 25 O2PNaSi,[M+Na] + =487.1259,found:487.1256.

[0069] Example 15: Synthesis of (S)-7-bis(p-methoxyphenyl)phosphino-7'-carboxy-1,1'-spirosilyldihydroindene:

[0070] Using (S)-7,7'-bis(p-methoxyphenyl)phosphino-7'-methoxyacyl-1,1'-spirosilyldihydroindene as a starting material, the method was the same as in Example 14. The product was a white solid. Yield: 80%, mp: 142-143℃, [α] D 25 = -198.2 (c = 1, CH2Cl2). 1 H NMR (400MHz, CDCl3) δ7.98 (dd, J=8.0, 1.2Hz, 1H), 7.55 (dt, J=7.5, 1.1Hz, 1H), 7.42 (dq, J=7.7, 1.0Hz, 1H),7.36–7.33(m,4H),7.32(dq,J=7.0,1.1Hz,1H),7.25–7.22(m,2H),6.97–6.89(m,4H),3.8(s,6H), 2.75(ddd,J=7.7,5.7,1.0Hz,1H),2.55(ddd,J=7.5,5.8,1.0Hz,1H),2.43(ddd,J=7.7,5.7,1.0Hz,1H) ,2.3(ddd,J=7.7,5.7,1.0Hz,1H),1.68(ddd,J=7.3,5.7,1.5Hz,2H),1.36(ddd,J=7.5,6.8,5.7Hz,2H). 13 C NMR (100MHz, CDCl3) δ172.0,160.2,153.7,144.8,142.3,138.2,137.6,136.3,135.9,1 30.2,129.2,128.1,126.9,126.4,126.0,122.4,114.7,55.3,32.86,32.0,14.6,14.7. 31 P NMR(161MHz,CDCl3)δ-11.8.HRMS(ESI)m / z calcd for C 31 H 29 O4PNaSi,[M+Na] + =547.1470,found:547.1473.

[0071] Example 16: Synthesis of (S)-7-bis(p-methylphenyl)phosphino-7'-carboxy-1,1'-spirosilyldihydroindene:

[0072] Using (S)-7,7'-bis(p-methylphenyl)phosphino-7'-methoxyacyl-1,1'-spirosilyldihydroindene as a starting material, the method was the same as in Example 14. The product was a white solid. Yield: 85%, mp: 155-156℃, [α]D 25 = -190.2 (c = 1, CH2Cl2). 1 H NMR (400MHz, CDCl3) δ7.86 (dd, J=8.0, 1.2Hz, 1H), 7.75 (dt, J=7.5, 1.1Hz, 1H), 7.6 6(dd,J=7.7,1.1Hz,1H),7.45(dd,J=7.1,1.1Hz,1H),7.35–7.28(m,6H),7.22–7.15 (m,4H),2.78(ddd,J=7.7,5.7,1.0Hz,1H),2.65(ddd,J=7.5,5.8,1.0Hz,1H),2.55 –2.43(m,8H),1.75(ddd,J=7.3,5.7,1.5Hz,2H),1.42(ddd,J=7.5,6.8,5.7Hz,2H). 13 C NMR (100MHz, CDCl3) δ169.0,153.7,144.9,142.3,138.7,138.2,137.5,135.9,134.9, 130.9,130.2,129.7,128.1,127.9,126.5,126.0,122.6,32.5,32.2,21.2,15.3,14.8. 31 P NMR(161MHz,CDCl3)δ-10.7.HRMS(ESI)m / z calcd for C 31 H 29 O2PNaSi,[M+Na] + =515.1572,found:515.1750.

[0073] Example 17: Synthesis of (S)-7-bis(3,5-dimethylphenyl)phosphino-7'-carboxyl-1,1'-spirosilyldihydroindene:

[0074] Using (S)-7,7'-bis(3,5-dimethylphenyl)phosphino-7'-methoxyacyl-1,1'-spirosilyldihydroindene as a starting material, the method was the same as in Example 14. The product was a white solid. Yield: 75%, mp: 134-135℃, [α] D 25 = -203.2 (c = 1, CH2Cl2). 1H NMR (400MHz, CDCl3) δ7.92(dd,J=8.0,1.2Hz,1H),7.82(dt,J=7.5,1.1Hz,1H),7.76(dd,J=7.7,1.1Hz,1H),7.65(dd,J=7.1,1.1Hz,1H),7 .55–7.35(m,6H),7.3–7.2(m,4H),3.64-3.56(m,2H),3.25-3.19(m,2H),2.36(s,6H),2.28(s,6H),1.21-1.14(m,2H),1.07-0.98(m,2H). 13 C NMR (100MHz, CDCl3) δ180.2,155.2(d,J=15.4Hz),146.0,145.5,143.1(d,J =8.1Hz),137.66(d,J=5.Hz),135.5(d,J=11.1Hz),134.1(d,J=11.1Hz),133 .6(d,J=19.9Hz),133.0(d,J=18.1Hz),130.6,129.8,129.0(d,J=6.2Hz),1 28.7(d,J=7.2Hz),126.4,31.9(d,J=8.6Hz),21.3,21.3,10.0(d,J=5.2Hz). 31 P NMR(161MHz,CDCl3)δ-8.27.HRMS(ESI)m / z calcd for C 33 H 33 O2PNaSi,[M+Na] + =543.1885,found:543.1883.

[0075] Example 18: (S) a Preparation of ,S)-7'-diphenylphosphino-[1,1']-spirosilyldihydroindene-oxazoline compounds:

[0076]

[0077] In a 100 mL single-necked flask, weigh (S)-7-diphenylphosphino-7'-carboxy-1,1'-spirosilydihydroindene (250 mg, 0.55 mmol), valine (180 mg, 1.75 mmol), HOBt (190 mg, 1.24 mmol), and DCC (332 mg, 1.66 mmol). Add 30 mL of dry THF, purge three times with nitrogen, and stir the reaction under a nitrogen atmosphere at room temperature. A large amount of white precipitate forms in the system. Monitor the reaction by TLC until complete. Quench the system with water, extract with ethyl acetate, dry the organic phase with anhydrous sodium sulfate, remove the solvent by rotary evaporation, and use it directly for the next reaction without further purification. Add DMAP (5 mg, 0.041 mmol) to the above reaction flask, purge three times with nitrogen, add 10 mL of redistilled and degassed CH2Cl2, and stir until homogeneous. The mixture was cooled to 0°C, and 0.34 mL of Et3N and 170 μL of MsCl were added sequentially. The mixture was stirred at 0°C for 30 min, and then 1.45 mL of Et3N was added. The mixture was allowed to rise naturally to room temperature and stirred overnight. The reaction was monitored by TLC until complete conversion. The reaction was quenched with water, extracted with ethyl acetate, separated, filtered, dried over anhydrous sodium sulfate, and the solvent was removed by rotary evaporation. The mixture was purified by silica gel column chromatography using a petroleum ether / ethyl acetate mixture (10:1) as the eluent to give the compound (Sa,S)-2-[(7'-diphenylphosphino)-1,1'-spirosilyldihydroindene-7-]-4-isopropyl-4,5-dihydrooxazole (300 mg, 52%). The product was a white, foamy solid. Mp 131-132°C, [α] D 25 = -213.2 (c 0.5, CH2Cl2). 1H NMR(400MHz, CDCl3)δ7.84(dd,J=7.2,1.2Hz,1H),7.65(dt,J=7.5,1.1Hz,1H),7.38–7.27(m,9H),7.26–7.22(m,1H),7 .13(dt,J=7.7,1.3Hz,4H),4.43(dd,J=12.4,4.9Hz,1H),4.36(dd,J=12.4,4.9Hz,1H),3.96(dddt,J=9.3,4.8,3.1,1. 5Hz,1H),2.88(ddd,J=7.7,5.7,1.0Hz,1H),2.63(ddd,J=7.5,5.8,1.0Hz,1H),2.42(dddd,J=22.2,7.5,5.7,0.9Hz,2H ),1.69–1.60(m,1H),1.56(ddd,J=7.5,5.7,0.9Hz,2H),1.35(dt,J=7.7,5.8Hz,2H),0.85(ddd,J=6.8,2.4,1.5Hz,6H). 13 CNMR (100MHz, CDCl3) δ170.4,153.7,144.99,139.4,137.8,137.5,136.9,136.7,134.0,130.2,1 28.5,128.3,128.1,128.0,124.3,123.1,122.4,72.2,72.1,32.8,32.3,32.0,18.3,15.6,15.7. 31 P NMR(161MHz,CDCl3)δ29.92.HRMS(ESI)m / z calcd forC 34 H 34 O2PNNaSi,[M+Na] + =570.1994,found:570.1995.

[0078] Example 19: (S) a Preparation of ,S)-2-[(7'-diphenylphosphino)-1,1'-spirosilydinium-7-]-4-benzyl-4,5-dihydrooxazole:

[0079] The product was prepared using (S)-7-diphenylphosphino-7'-carboxy-1,1'-spirosilyldihydroindene and phenylpropanol as starting materials, following the same method as in Example 18. The product was a white solid, yield: 80%, mp: 143-144℃. [α] D 25 = -204.2 (c 0.5, CH2Cl2). 1H NMR (400MHz, CDCl3) δ7.9 (dd, J=6.9, 1.2Hz, 1H), 7.84 (dd, J=7.2, 1.2Hz, 1H), 7.71–7.63 (m, 5H), 7.5 8–7.53(m,2H),7.52–7.45(m,5H),7.36(dq,J=7.6,1.0Hz,1H),7.29–7.20(m,6H),4.8–4.6(m,3H),3 .3(dddd,J=12.9,6.8,2.1,1.0Hz,1H),3.1–3.0(m,1H),2.85(dddd,J=7.5,5.8,1.0Hz,1H),2.53(ddd ,J=7.7,5.7,1.0Hz,1H),2.41(dddd,J=10.4,7.5,5.7,0.9Hz,2H),1.25(dddd,J=7.5,5.7,3.1Hz,4H). 13 C NMR (100MHz, CDCl3) δ169.8,140.4,139.5,137.99,137.8,137.7,137.2,134.7,133.0,132.2,131.8,129.1 ,128.8,128.5,128.4,128.3,128.1,127.0,125.7,124.3,123.1,73.0,68.2,41.8,32.6,32.0,14.7,14.7. 31 P NMR(161MHz,CDCl3)δ30.12.HRMS(ESI)m / z calcd forC 38 H 34 O2PNNaSi,[M+Na] + =618.1994,found:618.1996.

[0080] Example 20: (S) a Preparation of ,S)-2-[(7'-diphenylphosphino)-1,1'-spirosilydinium-7-]-4-phenyl-4,5-dihydrooxazole:

[0081] The product was prepared using (S)-7-diphenylphosphino-7'-carboxy-1,1'-spirosilydihydroindene and phenylglycine as starting materials, following the same method as in Example 18. The product was a white solid, yield: 65%, mp: 112-113℃. [α] D 25 = -180.2 (c = 0.5, CH2Cl2). 1H NMR (400MHz, CDCl3) δ7.99 (dd, J=6.9, 1.2Hz, 1H), 7.82 (dd, J=7.1, 1.1Hz, 1H), 7.70–7.63 (m, 5H ),7.58–7.45(m,7H),7.40–7.32(m,5H),7.30–7.25(m,2H),5.27(t,J=4.4Hz,1H),4.77(dd,J=1 2.4, 4.3Hz, 1H), 4.67 (dd, J=12.5, 4.2Hz, 1H), 2.63 (ddd, J=7.5, 5.8, 1.0Hz, 1H), 2.57 (ddd, J=7 .7,5.7,1.0Hz,1H),2.41(dddd,J=10.4,7.5,5.7,0.9Hz,2H),1.46(dddd,J=7.5,5.7,3.1Hz,4H). 13 C NMR (100MHz, CDCl3) δ170.5,141.5,140.4,138.6,137.8,137.7,137.3,134.7,133.0,132.2,131.8,128 .8,128.7,128.4,128.3,128.1,127.9,127.0,125.7,124.3,123.2,74.5,70.1,32.6,32.0,16.5,16.2. 31 PNMR(161MHz,CDCl3)δ28.12.HRMS(ESI)m / z calcd for C 37 H 32 O2PNNaSi,[M+Na] + =604.1838,found:604.1835.

[0082] Example 21: (S) a Preparation of ,S)-7'-bis(p-methylphenyl)phosphino-[1,1']-spirosilydin-7-]-4-benzyl-4,5-dihydrooxazole:

[0083] The product was prepared using (S)-7-bis(p-methylphenyl)-7'-carboxy-1,1'-spirosilydihydroindene and phenylpropanol as starting materials, following the same method as in Example 18. The product was a white solid, yield: 81%, mp: 150-151℃. [α] D 25 = -204.2 (c 0.5, CH2Cl2). 1H NMR (400MHz, CDCl3) δ7.99 (dd, J=6.9, 1.2Hz, 1H), 7.84 (dd, J=7.2, 1.2Hz, 1H), 7.67 (t, J=7.0Hz, 1H) ,7.59–7.54(m,4H),7.51(dq,J=7.1,1.1Hz,1H),7.36(dq,J=7.6,1.0Hz,1H),7.31–7.18(m,10H),4. 39–4.32(m,3H),3.06(ddq,J=12.9,6.7,1.0Hz,1H),2.98–2.87(m,1H),2.63(ddd,J=7.5,5.8,1.0Hz ,1H),2.57(ddd,J=7.7,5.7,1.0Hz,1H),2.46–2.36(m,8H),1.46(dddd,J=7.5,5.4,4.1,0.9Hz,4H). 13 C NMR (100MHz, CDCl3) δ169.8,140.8,140.4,139.5,137.9,137.8,137.7,137.2,134.7,132.7,129.9,129.2,12 9.0,128.8,128.5,128.3,128.1,127.0,125.7,124.3,123.1,73.0,68.2,41.8,32.6,32.0,21.2,18.1,16.7. 31 P NMR(161MHz,CDCl3)δ29.3.HRMS(ESI)m / z calcd forC 40 H 38 O2PNNaSi,[M+Na] + =646.2307,found:646.2301.

[0084] Example 22: (S) a Preparation of ,S)-7'-bis(p-methoxyphenyl)phosphino-[1,1']-spirosilydin-7-]-4-benzyl-4,5-dihydrooxazole:

[0085] The product was prepared from (S)-7-bis(p-methoxyphenyl)-7'-carboxy-1,1'-spirosilydihydroindene and phenylpropanol, using the same method as in Example 18. The product was a white solid, yield: 75%, mp: 146-147℃. [α] D 25 = -196.2 (c = 0.5, CH2Cl2). 1H NMR(400MHz, CDCl3)δ7.85(dd,J=6.9,1.2Hz,1H),7.76(dd,J=7.2,1.2Hz,1H),7.62–7.58(m,5H),7.55(dq, J=7.0,1.1Hz,1H),7.48(dq,J=7.7,1.0Hz,1H),7.41–7.36(m,6H),7.28–7.08(m,4H),4.8–4.6(m,3H),3.8(s ,6H),3.2(dddd,J=13.7,6.8,1.9,0.9Hz,1H),3.12–2.98(m,1H),2.83(dddd,J=7.5,5.8,1.0Hz,1H),2.72(dd d,J=7.7,5.7,1.0Hz,1H),2.53(dddd,J=10.4,7.5,5.7,0.9Hz,2H),1.65(dddd,J=7.5,5.4,4.1,0.9Hz,4H). 13 C NMR (100MHz, CDCl3) δ169.8,162.0,140.4,139.5,137.9,137.7,137.7,137.2,134.7,134.1,129.1,128.8,12 8.5,128.3,128.1,127.0,127.0,125.7,124.3,123.1,114.1,73.0,68.2,55.3,41.8,32.6,32.0,14.7,14.7. 31 P NMR(161MHz,CDCl3)δ31.2.HRMS(ESI)m / zcalcd for C 40 H 38 O4PNNaSi,[M+Na] + =678.2205,found:678.2201.

[0086] Example 23: (S) a Preparation of ,S)-7'-diphenylphosphino-[1,1']-spirosilydinium-7-]-4-isopropyl-4,5-dihydrooxazole ligand:

[0087]

[0088] Add (S)-7-(Sa,S)-7'-diphenylphosphino-[1,1']-spirosilydinium-7-]-4-isopropyl-4,5-dihydrooxazole (0.5 g, 0.5 mmol), diisopropylethylamine (2.6 g, 20 mmol), and 30 mL of toluene to a 100 mL sealed tube. After cooling to 0 °C, slowly add trichlorosilane (0.8 mL, 8 mmol) while stirring at 0 °C. Remove the ice bath and heat in an oil bath to 110 °C with stirring for 1 day. Cool to room temperature, dilute with ethyl acetate, quench the reaction with saturated ammonium chloride solution, filter, wash the filter cake with ethyl acetate, and dry with anhydrous sodium sulfate. After solvent removal by rotary evaporation, the solution was purified by silica gel column chromatography (elution buffer: petroleum ether / EtOAc = 30:1) to give (Sa,S)-7'-diphenylphosphino-[1,1']-spirosilydinium-7-]-4-isopropyl-4,5-dihydrooxazole ligand, 80% yield, white solid, mp: 77-78℃. [α] D 25 =-203.2(c=1.0, CH2Cl2), 1 H NMR(400MHz, CDCl3)δ7.7(dd,J=7.2,1.2Hz,1H),7.54(dt,J=7.5,1.1Hz,1H),7.42–7.37(m,9H),7.32–7.22(m,1H),7 .2(dt,J=7.7,1.3Hz,4H),4.6(dd,J=12.4,4.9Hz,1H),4.52(dd,J=12.4,4.9Hz,1H),4.12(dddt,J=9.3,4.8,3.1,1.5H z,1H),3.02(ddd,J=7.7,5.7,1.0Hz,1H),2.83(ddd,J=7.5,5.8,1.0Hz,1H),2.63(dddd,J=22.2,7.5,5.7,0.9Hz,2H) ,1.82–1.70(m,1H),1.63(ddd,J=7.5,5.7,0.9Hz,2H),1.42(dt,J=7.7,5.8Hz,2H),1.01(ddd,J=6.8,2.4,1.5Hz,6H). 13 C NMR (100MHz, CDCl3) δ168.4,154.7,145.9,140.4,138.8,138.5,137.9,137.7,135.0,131.2,12 9.5,129.3,129.1,129.0,125.3,124.1,123.4,73.2,73.1,33.8,33.3,33.0,19.3,16.6,16.7. 31P NMR(161MHz,CDCl3)δ-7.23.HRMS(ESI)m / zcalcd for C 34 H 34 OPNNaSi,[M+Na] + =554.2045,found:554.2043.

[0089] Example 24: (S) a Preparation of the ligand ,S)-7'-diphenylphosphino-[1,1']-spirosilydinium-7-]-4-benzyl-4,5-dihydrooxazole:

[0090] With (S) a The product was prepared from α-(1,1')-7'-diphenylphosphino-[1,1']-spirosilydinium-7-]-4-benzyl-4,5-dihydrooxazole as a starting material, using the same method as in Example 23. The product was a white solid, yield: 85%, mp: 82-83℃. D 25 = -215.2 (c = 0.5, CH2Cl2). 1 H NMR (400MHz, CDCl3) δ7.84 (dd, J=7.2, 1.2Hz, 1H), 7.65 (dt, J=7.5, 1.1Hz, 1H), 7.39–7 .19(m,15H),7.13(dt,J=7.7,1.3Hz,4H),4.40–4.32(m,3H),3.06(dddd,J=12.8,6.7,2 .1,1.0Hz,1H),2.96–2.87(m,1H),2.62(dddd,J=14.4,7.5,5.7,1.0Hz,2H),2.44(ddd, J=7.7,5.7,1.0Hz,1H),2.40(ddd,J=7.5,5.7,1.0Hz,1H),1.35(dt,J=7.6,5.7Hz,4H). 13 C NMR (100MHz, CDCl3) δ169.8,152.8,143.8,138.4,137.7,137.6,137.5,137.0,136.6,134.0,132.2,129.1 ,128.5,128.4,128.3,128.1,128.0,127.0,125.3,124.1,123.4,77.0,69.2,44.8,35.9,34.0,16.7,15.6. 31 P NMR(161MHz,CDCl3)δ-8.2.HRMS(ESI)m / z calcd for C 38 H 34OPNNaSi,[M+Na] + =602.2045,found:602.2043.

[0091] Example 25: (S) a Preparation of ,S)-7'-diphenylphosphino-[1,1']-spirosilydinium-7-]-4-phenyl-4,5-dihydrooxazole ligand:

[0092] With (S) a The product was prepared from α-(1,1')-7'-diphenylphosphino-[1,1']-spirosilydinium-7-]-4-phenyl-4,5-dihydrooxazole as a starting material, using the same method as in Example 23. The product was a white solid, yield: 85%, mp: 82-83℃. D 25 = -215.2 (c = 0.5, CH2Cl2). 1 H NMR (400MHz, CDCl3) δ8.01 (dd, J=7.1, 1.3Hz, 1H), 7.7 (dt, J=7.5, 1.1Hz, 1H), 7. 55–7.21(m,15H),7.23(dt,J=7.7,1.3Hz,4H),5.57(t,J=4.3Hz,1H),4.98(dd,J =12.4,4.3Hz,1H),4.88(dd,J=12.5,4.2Hz,1H),2.85(dddd,J=14.4,7.5,5.7,1 .0Hz,2H),2.63(dddd,J=22.2,7.5,5.7,0.9Hz,2H),1.55(dt,J=7.6,5.7Hz,4H). 13 C NMR (100MHz, CDCl3) δ170.5,153.7,144.9,141.5,138.6,137.8,137.5,137.1,136.7,134.0,130.2,128 .7,128.5,128.3,128.1,128.0,127.9,127.0,124.3,123.2,122.4,74.5,70.1,32.8,32.0,14.7,14.6. 31 P NMR(161MHz,CDCl3)δ-7.6.HRMS(ESI)m / z calcd forC 37 H 32 OPNNaSi,[M+Na] + =588.1888,found:588.1885.

[0093] Example 26: [(S aPreparation of BARF: [S)-Ph-Si-SIPHOX-Bn-Ir(COD)]

[0094]

[0095] Weigh the ligand (S) in the glove box. a ,S)-2-[(7-diphenylphosphino)-1,1'-spirosilydinium-7-]-4-benzyl-4,5-dihydrooxazole (58 mg, 0.1 mmol), [Ir(COD)Cl]2 (61 mg, 0.1 mmol), and NaBARF (170 mg) were placed in a 15 mL Schlenk reaction tube. After removal, freshly distilled CH2Cl2 (3 mL) was added using a syringe. The mixture was heated to 50 °C and reacted for 3 h. The reaction was monitored by TLC. The reaction was stopped when the ligands were completely complexed, and the mixture was allowed to cool naturally to room temperature. The mixture was diluted with CH2Cl2 (10 mL), dissolved by rotary evaporation, and the residue was purified by column chromatography to give an orange-yellow solid, yield 82%, mp: 182-183 °C, [α- D 25 =198.2 (c=0.5, CH2Cl2). 1 H NMR (400MHz, CDCl3) δ8.14–7.97(m,2H),7.78–7.70(m,8H),7.63(dt,J=15.0,7.0Hz,3H),7.58–7.47(m,7H),7.46–7.32( m,5H),7.27–7.17(m,5H),7.09(dt,J=8.9,4.1Hz,1H),6.87–6.80(m,2H),4.97(s,1H),4.14–4.03(m,1H),3.73(ddd,J=2 1.4,13.8,5.6Hz,3H),3.46–3.34(m,2H),3.27–2.99(m,4H),2.65(t,J=12.4Hz,1H),2.47–2.35(m,1H),2.11–1.94(m,2H ),1.59(s,2H),1.43–1.33(m,2H),1.16(ddd,J=16.0,9.4,7.1Hz,2H),1.00–0.87(m,4H),0.33(dt,J=14.8,10.0Hz,1H). 13C NMR (100MHz, CDCl3) δ170.9,162.4,161.9,161.4,160.9,151.9,137.6,136.4,136.3,134.8,134.5,133.8,1 33.7,132.6,131.8,131.5,131.4,130.9,130.4,130.3,129.9,129.4,129.3,129.2,129.2,129.1,129.0,12 9.0,129.0,128.7,128.7,128.6,128.4,128.2,127.8,125.9,124.6,123.2,120.4,117.4,117.4,93.3,93.2,89.1,89.0,67.9,66.1,64.9,62.2,41.8,33.2,33.2,32.3,30.7,29.7,29.3,25.9,19.0,13.6,12.9,10.9. 31 P NMR(161MHz,CDCl3)δ11.41.HRMS(ESI)m / z calcd for C 46 H 46 OPNIrSi,[M+H] + =880.2710,found:880.2706.

[0096] Example 27: [(S a Preparation of BARF: [S)-Ph-Si-SIPHOX-Ph-Ir(COD)]

[0097] The product was prepared using (Sa,S)-2-[(7'-diphenylphosphino)-1,1'-spirosilyldihydroindene-7-]-4-phenyl-4,5-dihydrooxazole and [Ir(COD)Cl]2 as raw materials, following the same method as in Example 26. The product was a yellow, foamy solid, yield: 75%, mp 158-159℃, [α] D 25 =192.2 (c=0.5, CH2Cl2). 11H NMR (400 MHz, CDCl3) δ 8.6–8.2 (m, 4H), 8.1–7.8 (m, 11H), 7.72 (dt, J = 15.0, 7.0 Hz, 3H), 7.6–7.57 (m, 7H), 7.5–7.4 (m, 5H), 7.3–7.2 (m, 5H), 7.1 (dt, J = 8.9, 4.1 Hz, 1H), 7.0–6.92 (m, 2H), 4.6 (s, 1H), 4.3–4.12 (m, 1H), 3.56 (ddd, J = 21.4, 13.8, 5.6 Hz, 3H), 3.52–3.46 (m, 2H), 2.36 (s, 6H), 3.32–3.12 (m, 4H), 2.86 (t, J = 12.4 Hz, 1H), 2.63–2.45 (m, 1H), 2.32–2.01 (m, 2H), 1.8 (s, 2H), 1.53–1.43 (m, 2H), 1.2 (ddd, J = 16.0, 9.4, 7.1 Hz, 2H), 0.99–0.87 (m, 4H), 0.43 (dt, J = 14.8, 10.0 Hz, 1H). 13 13C NMR (100 MHz, CDCl3) δ 172.8, 163.7, 162.2, 161.7, 161.2, 149.6, 148.5, 148.4, 148.3, 145.4, 142.4, 139.​​​​​​​​​​​​​​Preparation of Pr-Ir(COD)]BARF:

[0099] With (S) a The product was prepared from (S)-2-[(7'-diphenylphosphino)-1,1'-spirosilyldihydroindene-7-]-4-phenyl-4,5-dihydrooxazole and [Ir(COD)Cl]2, using the same method as in Example 26. The product was a yellow, foamy solid, yield: 78%, mp 145-146℃, [α-] D 25 =198.2 (c=0.5, CH2Cl2). 1 H NMR (400MHz, CDCl3) δ7.85-7.72(m,8H),7.63-7.43(m,18H),7.28-7.22(m ,2H),4.70-4.58(m,1H),4.56-4.32(m,2H),3.84-3.74(m,1H),3.72-3.65 (m,1H),3.50-3.52(m,1H),2.8-2.72(m,2H),2.51-2.39(m,1H);2.37-2.1 4(m,5H),2.01-1.91(m,2H),1.72(d,J=6.8Hz,3H),0.55(d,J=6.6Hz,3H); 13 C NMR (100MHz, CDCl3) δ173.6,162.5,162.1,161.6,161.2,149.6,149.5,148.4,148.2,146.0,1 37.8,137.6,136.0,135.6,134.8,133.6,133.1,132.1,130.7,130.5,130.3,130.1,130.0,12 9.7,129.6,129.4,129.3,128.5,127.9,127.5,125.1,124.4,122.7,118.6,86.0,85.8,84.6,84.5,75.4,73.2,72.7,68,6,66.9,45.0,38.1,35.0,33.3,32.6,31.0,29.8,28.8,25.7,19.2; 31 P NMR(161MHz,CDCl3)δ12.1.HRMS(ESI)m / z calcd for C 42 H 47 OPNIrSi,[M+H] + =833.2788,found:833.2785.

[0100] Example 29: Enantioselective hydrogenation of α,β-unsaturated carboxylic acids:

[0101] (with [(S) a [S)-Ph-Si-SIPHOX-Bn-Ir(COD)]BARF (using the catalytic hydrogenation of 2-methyl-3-phenylacrylic acid prepared in Example 26 as an example)

[0102]

[0103] In a glove box, 3.7 mg (0.2 mol%) of catalyst [(Sa,S)-Si-SIPHOX-Bn-Ir(COD)]BARF and 324 mg (2 mmol) of 2-methyl-3-phenylacrylic acid were weighed into a 15 mL Schlenk reaction tube equipped with a stir bar and sealed with a rubber stopper. After removal, methanol (5 mL) and triethylamine (0.1 mL) were added using a syringe. The mixture was then purged with N2 gas three times in a double-row tube, and finally, the system was replaced with hydrogen gas (6 atm) to form an H2 atmosphere. The reaction was maintained at 25 °C for 24 hours. Stirring was stopped, and the reaction was monitored by TLC. The reaction solution was concentrated by rotary evaporation and purified by silica gel column chromatography using petroleum ether / ethyl acetate (2 / 1) as the eluent, yielding a colorless oily substance with a yield of 60%. The ee value was analyzed by chiral HPLC. HPLC test conditions: Chiralpak AS column (25cm × 0.46cm ID), n-hexane / 2-propanol = 95:5, 1.0 mL / min, 254nm UV detector, t R of(S)-isomer 18.14min,t R of(R)-isomer 22.03min.93%ee, [α] D 25 =25.3 (c=0.5, CH2Cl2). 1 HNMR (400MHz, CDCl3): δ9.95(brs,1H,COOH),7.31-7.18(m,5H,Ar-H),3.08(dd,J=13.2and6.4Hz,1H),2.77(m,1H),2.67(dd,J=13.2and 8.0Hz,1H),1.18(d,J=6.8Hz,3H). 13 C NMR(100MHz, CDCl3)δ182.0,138.9,128.9,128.4,126.8,41.3,39.3,16.5.HRMS(ESI)m / zcalcd for C 10 H 14 O2, [M+H] +=165.0915found:165.0913.

[0104] The test results of the enantioselective hydrogenation reaction of the catalysts prepared in Examples 26, 27 and 28 are shown in Table 1.

[0105] Table 1

[0106]

Claims

1. A silicospirocyclic phosphine-oxazoline compound having a spirosilyl dihydroindene structure, characterized in that, Specific structural formula: ； Among them, R 1 It is a C1-C6 hydrocarbon group, phenyl, substituted phenyl, 1-naphthyl, 2-naphthyl, benzyl; the hydrocarbon group is methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl; the hydroxyl group is methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy; R 2 It includes C1~C6 hydrocarbon groups, phenyl groups, substituted phenyl groups, 1-naphthyl groups, 2-naphthyl groups, and benzyl groups; The substituents on the phenyl group are C1-C6 hydrocarbon groups, hydroxyl groups, and haloalkyl groups, with the number of substituents ranging from 1 to 5.

2. The silicospirocyclic phosphine-oxazoline compound according to claim 1, characterized in that, It is the dextrorotatory silicospirophosphine-oxazoline ligand -(R, R)-2-[(7'-diarylphosphino)-1,1'-spirosilydinium-7-]-4-substituted-4,5-dihydrooxazole or (S, R)-2-[(7'-diarylphosphino)-1,1'-spirosilydinium-7-]-4-substituted-4,5-dihydrooxazole, and the levorotatory silicospirophosphine-oxazoline ligand (S, S)-2-[(7'-diarylphosphino)-1,1'-spirosilydinium-7-]-4-substituted-4,5-dihydrooxazole or (R, S)-2-[(7-diarylphosphino)-1,1'-spirosilydinium-7-]-4-substituted-4,5-dihydrooxazole; The silicospirophosphine-oxazoline compounds have two chiral factors: axial chirality and central chirality.

3. An ionic iridium complex using the silicospirophosphine-oxazoline compound of claim 1 or 2 as a ligand, characterized in that, The structural formula is: ； X - It is hexafluorophosphate, hexafluorotellurate, tetrafluoroborate, tetraphenylborate or tetra-(3,5-ditrifluoromethylphenyl)borate.

4. A method for synthesizing a silicospirocyclic phosphine-oxazoline compound as described in claim 1 or 2, characterized in that, Starting with optically pure 1,1'-spirosilydinium-7,7'-diol, the reaction proceeds with trifluoromethanesulfonic anhydride to form trifluoromethanesulfonate, followed by palladium-catalyzed coupling with a phosphine oxide. The phosphine oxide is then reduced by trichlorosilane to generate the intermediate 7-diarylphosphino-7'-trifluoromethanesulfonyloxy-1,1'-spirosilydinium. This intermediate then undergoes palladium-catalyzed carbonylation esterification, followed by hydrolysis of the ester to an acid under alkaline conditions. The acid is then condensed with a 2-substituted chiral aminoethanol to form an amide alcohol, which is subsequently cyclized to obtain a silicospirophosphine oxide-oxazoline ligand. Finally, reduction with trichlorosilane yields the silicospirophosphine oxide-oxazoline ligand. The specific steps are as follows: (1) Using 1-4 equivalents of trifluoromethanesulfonic anhydride and 1 equivalent of optically pure 1,1'-spirosilydinium-7,7'-diol as raw materials, and 2-6 equivalents of pyridine as an acid-binding agent, the corresponding bis(trifluoromethanesulfonate) compounds are generated by reaction at a temperature of 0℃ to 30℃, and the solvent used is dichloromethane, dichloroethane, toluene or tetrahydrofuran; (2) The compound obtained in step (1) is reacted with 5-15 equivalents of organic amine and 1-3 equivalents of diarylphosphine oxide for 1-12 hours under the catalysis of 1-10 mol% palladium acetate and 1-15 mol% 1,4-bis(diphenylphosphine)butane to obtain a monophosphine-substituted product. The reaction solvent is dimethyl sulfoxide or N,N-dimethylformamide; the reaction temperature is 80-150℃. (3) The compound obtained in step (2) is reduced with 15 to 50 equivalents of trichlorosilane reducing agent in the presence of 15 to 40 equivalents of organic amine for 1 to 3 days to obtain monophosphine reduction product. The reaction solvent is toluene or xylene, and the reaction temperature is 90 to 120°C. (4) The compound obtained in step (3) is reacted with 2-15 equivalents of organic amine and methanol in carbon monoxide for 1-24 hours under the catalysis of 1-10 mol% palladium acetate and 1-15 mol% 1,3-bis(diphenylphosphine)propane to obtain a unilateral esterification product. The reaction solvent is dimethyl sulfoxide or N,N-dimethylformamide, and the reaction temperature is 25℃-100℃. (5) The esterification product obtained in step (4) is hydrolyzed in the presence of 30-60% potassium hydroxide aqueous solution to generate acid; the solvent used is methanol or ethanol; the reaction temperature is 50-100℃. (6) The product obtained in step (5) is condensed with 2-4 equivalents of 2-substituted chiral 2-aminoethanol in the presence of 2-4 equivalents of 1-hydroxybenzotriazole and 3-6 equivalents of N,N-dicyclohexylcarbamate for 1-12 hours to obtain the corresponding amide alcohol compound. The solvent used is diethyl ether, tetrahydrofuran or dioxane, and the reaction temperature is 0-50℃. (7) The amide alcohol compound obtained in step (6) is reacted with 2-20% N,N-dimethyl-4-aminopyridine as a catalyst, with 2-4 equivalents of organic base as an acid-binding agent, and 1-1.5 equivalents of methanesulfonyl chloride, ethanesulfonyl chloride or p-toluenesulfonyl chloride as a chlorinating agent to obtain a chiral silicospirocyclic phosphono-oxazoline compound. The solvent used is dichloromethane or 1,2-dichloroethane, and the organic base is triethylamine, tetramethylethylenediamine or diisopropylethylamine. The reaction temperature is 0℃~50℃. (8) The silicospirophosphine-oxazoline compound obtained in step (7) is reduced with 15-40 equivalents of trichlorosilane reducing agent for 1-3 days in the presence of 15-50 equivalents of organic amine to obtain chiral silicospirophosphine-oxazoline compounds. The reaction solvent is toluene or xylene, and the reaction temperature is 90-120℃.

5. The synthesis method according to claim 4, characterized in that: In steps (2), (3), (4), and (8), the organic amine is diisopropylethylamine, tetramethylethylenediamine, triethylamine, n-butylamine, or N,N-diethylaniline; In step 7, the organic base is triethylamine, tetramethylethylenediamine, or diisopropylethylamine.

6. A method for preparing the ionic iridium complex as described in claim 3, characterized in that, The silicospirophosphine-oxazoline compound of claim 1 or 2 is reacted with 1-2 equivalents of a monovalent iridium compound [Ir(COD)Cl]2, wherein COD = 1,5-cyclooctadiene, and 1-3 equivalents of sodium salts with different anions for 1-20 hours to obtain the corresponding ionic iridium complex; the solvent used is chloroform, dichloromethane or 1,2-dichloroethane, and the reaction temperature is 25℃-50℃.

7. The application of the ionic iridium complex as described in claim 3 as a catalyst in the catalytic hydrogenation reaction of a prochiral compound containing a carbon-carbon double bond.

8. The application according to claim 7, characterized in that, The catalytic hydrogenation process is as follows: Under argon or nitrogen protection, the catalyst and substrate are added to the inner tube of the hydrogen reactor, followed by the addition of degassed solvent. The reactor is then tightened and purged with hydrogen 3-5 times. After the hydrogen pressure is increased to the required level, the reaction is stirred until the reaction is complete. The catalyst dosage is 1%-0.05%, the hydrogen pressure is 1-50 atm, the reaction temperature is 0-60℃, the reaction time is 1 hour-48 hours, and the reaction solvent is chloroalkanes, benzene, toluene, alcohols, or ethers.

9. The application according to claim 8, characterized in that, During the catalytic hydrogenation process, one or more of the following are added as additives: triethylamine, tetramethylethylenediamine, diisopropylamine, diisopropylethylamine, cesium carbonate, potassium carbonate, and potassium tert-butoxide.

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