Novel chiral ferrocene bridged binaphthalene skeleton phosphine ligand and application thereof

Abstract

The invention provides a novel chiral ferrocene bridged binaphthyl skeleton phosphine ligand and application thereof. The ligand has the advantages of low cost, simplicity in synthesis, air stability and the like. The ligands have good catalytic activity and enantioselectivity in the asymmetric hydrogenation reaction of ketone, and have certain industrial application prospects in the synthesis of pharmaceutical molecules.

Description

Technical Field

[0001] The invention belongs to the field of chemical industry, and particularly relates to a novel chiral ferrocene-bridged binaphthyl skeleton phosphine ligand and application thereof. Background Art

[0002] Asymmetric hydrogenation of prochiral ketones is a direct and efficient method for synthesizing chiral alcohols. The key lies in developing stable, efficient, and broad-spectrum chiral phosphine ligands to precisely recognize prochiral ketones. Since the development of ligands by Professors Noyori, Zhang Xumu, Zhou Qilin, and Zhang Wanbin, this field has experienced rapid progress. However, existing ligands remain insufficient for chiral recognition of some prochiral ketones, limiting their widespread application. Therefore, the development of novel chiral phosphine ligands and catalytic systems remains of great value. Summary of the Invention

[0003] In order to achieve the technical purpose of the present invention, the technical solution of the present invention is: First, the present invention provides a novel chiral ferrocene-bridged binaphthyl skeleton phosphine ligand, specifically, a chiral ferrocene-bridged binaphthyl skeleton phosphine ligand shown in Formula I is provided: , Provided is a chiral ferrocenium-bridged binaphthyl skeleton phosphine ligand shown in formula II: , Provided is a chiral ferrocenium-bridged binaphthyl skeleton phosphine ligand shown in formula III: , Provided is a chiral ferrocene-bridged binaphthyl skeleton phosphine ligand shown in formula IV: , in: Ar in the chiral ferrocene-bridged binaphthyl skeleton phosphine ligand shown in formula I-IV is an aryl group or a substituted aryl group; R in Formula I-IV 1 One independently selected from hydrogen, aryl, alkyl, fluorine, chlorine, bromine, iodine, and alkoxy; R in Formula I-IV 2 Independently selected from one of NH2, NHMe, NMe2, NHAc, NHCOAr, NHSO2Me, NHSO2CF3, and NHSO2Ar, wherein Ar is an aryl group or a substituted aryl group.

[0004] The Ar is preferably phenyl, and the R 1 More preferably, it is hydrogen, and the R 2 More preferred are NH2, NMe2, and NHSO2Ar, wherein Ar is a substituted aryl group.

[0005] Most preferably, the chiral ferrocene-bridged binaphthyl skeleton phosphine ligand has the structural formula: , , .

[0006] In a second aspect, the present invention provides a method for preparing a chiral ferrocenium-bridged binaphthyl skeleton phosphine-type III ligand, the reaction formula is as follows: , Among them, Ar, R 1 、R 2 The definition of is the same as above.

[0007] in, （S) -DI-NH2 and (S c ,R Fc ) The solvent for the addition reaction is an organic solvent, preferably methanol.

[0008] in, （S) -DI-NH2 and (S c ,R Fc ) The temperature range of the -1 addition reaction is 50~70℃, preferably 60℃.

[0009] More preferably, the chiral ferrocene-bridged binaphthyl skeleton phosphine ligand (S c ,S ax ,R Fc ) -L1 is prepared as follows: .

[0010] In a third aspect, the present invention provides a catalyst for asymmetric hydrogenation, prepared by complexing the chiral ferrocenium-bridged binaphthyl phosphine ligand with a transition metal or its salt. The transition metal is selected from the group consisting of Ru (ruthenium), Rh (rhodium), Pd (palladium), Ir (iridium), Fe (iron), Co (cobalt), Ni (nickel), Cu (copper), Sc (scandium), Ti (titanium), Cr (chromium), Mn (manganese), Re (rhenium), Os (osmium), and Pt (platinum).

[0011] Wherein, the transition metal salt is RuX3 (Chinese expression: trivalent ruthenium salt), RuHX(L)2(Diphosphine) (Chinese expression: diphosphine ruthenium hydrogen complex), RuX2(L)2(Diphosphine) (Chinese expression: diphosphine divalent ruthenium complex), Ru(arene)X2(Diphosphine) (Chinese expression: diphosphine diaryl divalent ruthenium complex), Ru(aryl group)X2 (Chinese expression: disubstituted aryl divalent ruthenium complex), Ru(RCOO)2(Diphsphine) (Chinese expression: diphosphine disubstituted carboxyl divalent ruthenium complex), Ru(methallyl)2(Diphosphine) (Chinese expression: diphosphine bis(methallyl) ruthenium complex), Ru(aryl group)X2(PPh3)3 (Chinese description: substituted aryl tris(triphenylphosphine) ruthenium complex), Ru(COD)(COT) (Chinese description: (1,5-cyclopentadiene)(1,3,5-cyclooctatriene) ruthenium), Ru(COD)(COT)X (Chinese description: (1,5-cyclopentadiene)(1,3,5-cyclooctatriene) ruthenium salt), RuX2(Cymene) (Chinese description: p-cymene divalent ruthenium complex), RuCl(COD) n(Chinese description: (1,5-cyclooctadiene) ruthenium chloride polymer), Ru(aryl group)X2(Diphosphine) (Chinese description: Disubstituted arylbisphosphine ruthenium salt complex), Ru(ArH)Cl2 (Chinese description: Dichloroaryl ruthenium complex), Ru(COD)(methallyl)2 (Chinese description: Bis(methallyl)(1,5-cyclooctadiene)ruthenium), Rh(CO)2Cl2 (Chinese description: Dicarbonyl rhodium dichloride), [Rh(NBD)2]BF4 (Chinese description: Bisnorbornadiene rhodium tetrafluoroborate), [Rh(NBD)Cl]2 (Chinese description: Norbornadiene rhodium chloride dimer), [Rh(COD)Cl]2 (Chinese description: (1,5-cyclooctadiene) rhodium chloride dimer), [Rh(COD)2]X (Chinese description: (1,5-cyclooctadiene) rhodium salt), Rh(acac)(CO)2 (Chinese description: Dicarbonyl acetylacetonate rhodium), Rh(ethylene)2(acac) (Chinese description: acetylacetonate di(ethylene) rhodium), [Rh(ethylene)2Cl]2 (Chinese description: di(ethylene) rhodium chloride dimer), RhCl(PPh3)3 (Chinese description: tri(triphenylphosphine) rhodium chloride), PdX2 (Chinese description: divalent palladium salt), Pd(PPh3)4 (Chinese description: tetra(triphenylphosphine) palladium), Pd(allyl)Cl (Chinese description: allylpalladium chloride), IrX3 (Chinese description: trivalent iridium salt), [Ir(NBD)2)Cl]2 (Chinese description: bis(norbornadiene) iridium chloride dimer), [Ir(COD)Cl]2 (Chinese description: (1,5-cyclooctadiene) iridium chloride), Ir(COD)X (Chinese description: (1,5-cyclooctadiene) iridium salt), FeX2 (Chinese description: divalent iron salt), FeX3 (Chinese description: trivalent iron salt), Ni(acac)2 (Chinese description: nickel (II) acetylacetonate), NiX2 (Chinese description: divalent nickel salt), [Ni(allyl)X]2 (Chinese description: allyl nickel dimer), Ni(COD)2 (Chinese description: bis-(1,5-cyclooctadiene) nickel), CuX (Chinese description: monovalent copper salt), CuX2 (Chinese description: divalent copper salt), MoO2(acac)2 (Chinese description: molybdenum acetylacetonate), ScX2 (Chinese description: divalent scandium salt), Ti(O i Pr)4 (Chinese expression: tetraisopropyl titanate), CrX2 (Chinese expression: divalent chromium salt), CrX3 (Chinese expression: trivalent chromium salt), MnBr(CO)5 (Chinese expression: pentacarbonyl manganese bromide), Mn2(CO) 10(Chinese description: dimanganese decacarbonyl), MnX2 (Chinese description: divalent manganese salt), Mn(acac)2 (Chinese description: manganese(II) acetylacetonate), or MeReO3 (Chinese description: methyl rhenium trioxide). Wherein, X is independently selected from one of Cl-, Br-, I-, ClO4-, BF4-, Sb6-, PF6-, CF3SO3-, RCOO-, and BAr4-; L is a solvent molecule such as MeCN or DMSO; and R is independently selected from one of an alkyl group, an alkoxy group, or a substituted alkyl group. Wherein, Ru represents metallic ruthenium, Diphosphine represents a diphosphine ligand, arene and ArH represent aromatic groups, aryl group represents a substituted aromatic group, Methallyl represents a methylallyl group, PPh3 represents triphenylphosphine, COD represents 1,5-cyclooctadiene, COT represents 1,3,5-cyclooctatriene, Cymene represents p-cymene, Rh represents metallic rhodium, CO represents a carbonyl group, NBD represents norbornadiene, acac represents acetylacetone, ethylene represents ethylene, Pd represents metallic palladium, allyl represents an allyl group, Ir represents metallic iridium, Fe represents metallic iron, Ni represents metallic nickel, Cu represents metallic copper, Mo represents metallic molybdenum, Sc represents metallic scandium, Ti represents metallic titanium, Cr represents metallic chromium, Mn represents metallic manganese, Me represents a methyl group, and Re represents metallic rhenium.

[0012] Preferably, the catalyst is an Ir complex formed by the complexation of a chiral ferrocenium-bridged binaphthyl skeleton phosphine ligand and an Ir metal salt.

[0013] The present invention provides the use of the chiral ferrocenyl-bridged binaphthyl skeleton phosphine ligand in the asymmetric hydrogenation of prochiral ketone compounds to synthesize chiral alcohol compounds. Specifically, under a nitrogen atmosphere, a metal salt, the ligand, and a solvent are added and stirred to form a clear solution. Subsequently, a base, a prochiral ketone compound, and a solvent are added to the reaction solution, and the reaction is carried out under hydrogen conditions.

[0014] The metal salt is defined as above. The ligand is defined as above.

[0015] Wherein, the solvent is an organic solvent, and anhydrous tetrahydrofuran is more preferred.

[0016] Wherein, the base is a strong base, preferably potassium tert-butoxide.

[0017] The reaction temperature of the asymmetric hydrogenation reaction is 10-60°C, preferably 20-30°C.

[0018] The reaction time of the asymmetric hydrogenation reaction is 30 to 60 hours, preferably 48 hours.

[0019] More preferred is the use of chiral ferrocenyl-bridged binaphthyl skeleton phosphine ligands in the asymmetric hydrogenation of acetophenone to synthesize 1-phenylethanol.

[0020]

[0021] The beneficial effects of the present invention are: the ligand provided by the present invention is simple to synthesize, low in cost and easy to scale up; the metal complex of the ligand exhibits good catalytic activity and good enantioselectivity in the process of asymmetric hydrogenation of prochiral ketone compounds to synthesize chiral alcohols, and has certain industrial application potential in asymmetric hydrogenation reactions. DETAILED DESCRIPTION

[0022] To further understand the present invention, the novel chiral ferrocenyl-bridged binaphthyl skeleton phosphine ligand provided by the present invention and its application are described in detail below with reference to the examples. It should be understood that these examples are only intended to further illustrate the features of the present invention and are not intended to limit the scope of the present invention or the scope of the claims.

[0023] The reagents used in the present invention can all be purchased from the market.

[0024] In the present invention, mmol represents millimole, h represents hour, g represents gram, L represents liter, and ml represents milliliter.

[0025] Example 1: Synthesis of ligand L1

[0026] （S) -Synthesis of DI-NH2: Add to 250ml flask （S ax ） -BINOL (5.00 g, 17.4 mmol), 2-bromopropionamide (7.96 g, 52.2 mmol), potassium carbonate (7.21 g, 52.2 mmol) and potassium iodide (33 mg, 0.20 mmol) were added, followed by the addition of dimethyl sulfoxide (30 mL) and stirring. The reaction solution was heated to 50-55°C and stirred until the raw material reaction was completely converted (TLC detection, generally 24 hours). The temperature was lowered to 20-30°C, potassium hydroxide (15.3 g, 217.5 mmol, 80%) was added, and the reaction solution was then heated to 145-150°C and stirred for 4 hours. The reaction solution was cooled to 0°C and quenched by the addition of 100 mL of water. The reaction solution was extracted with ethyl acetate (100 mL × 3), dried over sodium sulfate, filtered, concentrated, and separated by column chromatography. The eluent was then concentrated and dried to obtain (S ax )-DI-NH2 was a light brown solid, totaling 3.96 g, with a molar yield of 80%.

[0027] 1 H-NMR (400 MHz, CDCl3) δ 7.84-7.78 (m, 4H),7.27-7.18 (m, 4H),7.15 (d, J = 8.8 Hz, 2H), 7.09 (d, J = 8.1 Hz, 2H), 3.69 (brs, 4H). (S c ,R Fc ) -1 Synthesis: Add to 100ml flask （S c ） -1 (2.57 g, 10 mmol) and anhydrous ether (100 mL) were nitrogen-purged three times, then cooled to 0-5°C and sec-butyllithium solution (8.5 m, 11 mmol, 1.3 M) was added dropwise at 0-5°C, stirring for 0.5 hours, then heated to 20-30°C and stirred for 1.5 hours. The reaction solution was cooled to 0-5°C and diphenylphosphine chloride (2.65 g, 12 mmol) was added dropwise at 0-5°C, stirring for 16 hours at 20-30°C. The reaction solution was quenched by adding 200 mL of water, extracted with ethyl acetate (200 mL × 3), dried over sodium sulfate, filtered, concentrated, and separated by column chromatography. The eluent was then concentrated and dried to obtain (S c ,R Fc ) -1 was obtained as an orange solid, with a total weight of 3.08 g and a molar yield of 70%.

[0028] 1 H-NMR (400 MHz, CDCl3) δ 7.59 (dq, J = 7.5, 3.0, 2.0 Hz, 2H), 7.40-7.31(m, 3H), 7.23-7.12 (m, 5H), 4.36 (q, J = 2.0 Hz, 1H), 4.24 (t, J = 2.4 Hz, 1H),4.15 (dd, J = 6.8, 2.8 Hz, 1H), 3.94 (s, 5H), 3.85 (dt, J =2.4, 1.2 Hz, 1H),1.77 (s, 6H), 1.25(d, J = 6.8 Hz, 3H). (S c ,S ax ,R Fc ) -Synthesis of L1: Add to 10ml flask (S c ,R Fc ) -1 (441 mg, 1 mmol) and acetic anhydride (3 mL) were nitrogen purged three times, and then the internal temperature was raised to 100-105 ° C and stirred for 4-5 hours (TLC detection reaction until the raw material point disappears). After the reaction is completed, the reaction solution was cooled to 20-30 ° C, the solvent was dried, and toluene (10 mL × 3) was added and evaporated three times. The residue was added (S) -DI-NH2 (284 mg, 1 mmol) and 10 mL of methanol were stirred at 60°C for 16-24 hours. The reaction solution was filtered, and the filter cake was dissolved in 50 mL of dichloromethane, concentrated, and then subjected to column chromatography. The eluent was then concentrated and dried to obtain (S c ,S ax ,R Fc ) -L1 was a light yellow solid, with a total weight of 448 mg and a molar yield of 63%.

[0029] 1 H-NMR (400 MHz, DMSO- d 6) δ 7.91-7.84 (m, 3H), 7.81-7.75 (m, 1H), 7.43-7.28 (m, 5H), 7.24-7.15 (m, 4H), 7.14-7.08 (m, 3H), 7.07-7.00 (m, 4H),6.86-6.75 (m, 2H), 5.07 (dd, J = 10.1, 7.2 Hz, 1H), 4.71-4.57 (m, 3H), 4.35 (q, J = 1.9 Hz, 1H), 4.19 (t, J = 2.5 Hz, 1H), 3.57 (s, 5H), 3.54 (s, 1H), 1.21 (d, J= 6.4 Hz, 3H). 31 P-NMR (162 MHz, DMSO- d 6) δ -25.03.

[0030] Example 2: (S c ,S ax ,R Fc ) -L2 synthesis

[0031] Add to 10ml flask (S c ,S ax ,R Fc ) -L1 (712 mg, 1 mmol), triethylamine (202 mg, 2 mmol), 4-dimethylaminopyridine (12 mg, 10 mol%), and dichloromethane (5 mL) were stirred at 0-10°C. p-Toluenesulfonyl chloride (380 mg, 2 mmol) was added dropwise at an internal temperature of 0-10°C. After addition, the mixture was warmed to room temperature and allowed to react for 24 hours until the reaction of the raw materials was complete. The reaction solution was concentrated and then separated by column chromatography. The eluent was concentrated and dried to obtain (S c ,S ax ,R Fc ) -L2 was a light yellow solid, 493 mg in total, with a molar yield of 57%.

[0032] 1 H-NMR (400 MHz, DMSO- d 6) δ 8.11 (d, J = 9.0 Hz, 1H), 8.05 (d, J = 8.2 Hz,1H), 8.00 -7.87 (m, 3H), 7.80 (d, J = 8.0 Hz, 1H), 7.49 (ddd, J = 8.1, 6.8, 1.2Hz, 1H), 7.45 -7.40 (m, 2H), 7.41-7.29 (m, 4H), 7.27-7.09 (m, 7H), 7.08-6.97(m, 4H), 6.91 (ddd, J= 8.1, 6.7, 1.3 Hz, 2H), 6.18 (d, J = 8.4 Hz, 1H), 4.91 (t, J = 8.2 Hz, 1H), 4.68 (dd, J = 9.1, 6.4 Hz, 1H), 4.35 (q, J = 1.9 Hz, 1H), 4.20(t, J = 2.5 Hz, 1H), 3.58-3.46 (m, 6H), 2.31 (s, 3H), 1.27 (d, J = 6.4 Hz, 3H). 31 P-NMR (162 MHz, DMSO- d 6) δ -25.50.

[0033] Example 3: (S c ,S ax ,R Fc ) -Synthesis of L3

[0034] Add to 10ml flask (S c ,S ax ,R Fc ) -L1 (712 mg, 1 mmol), iodomethane (426 mg, 3 mmol), potassium carbonate (691 mg, 5 mmol) and anhydrous acetonitrile (5 mL) were stirred at 75-82°C until the reaction of the raw materials was complete. The reaction solution was concentrated and then subjected to column chromatography separation. The eluent was concentrated and dried to obtain (S c ,S ax ,R Fc ) -L3 was obtained as a light yellow solid, with a total weight of 229.4 mg and a molar yield of 31%.

[0035] 1 H NMR (400 MHz, DMSO- d 6) δ 8.09 (d, J = 9.0 Hz, 1H), 8.03 (d, J= 8.1 Hz,1H), 7.88 (d, J = 9.0 Hz, 1H), 7.80-7.74 (m, 1H), 7.64 (d, J = 9.0 Hz, 1H), 7.43-7.34 (m, 4H), 7.33-7.28 (m, 2H), 7.20-7.07 (m, 6H), 7.02 (d, J = 8.6 Hz, 1H), 6.96-6.89 (m, 4H), 6.79 (dt, J = 6.3, 3.1 Hz, 1H), 5.33 (t, J = 9.5 Hz, 1H), 4.42(q, J = 1.9 Hz, 1H), 4.23 (dt, J = 7.8, 2.5 Hz, 1H), 3.74 (s, 1H), 3.55-3.42 (m,5H), 2.42 (s, 6H), 1.15 (d, J = 6.4 Hz, 3H). 31 P-NMR (162 MHz, DMSO- d 6) δ -25.14.

[0036] Example 4: Asymmetric hydrogenation of acetophenone

[0037] Under nitrogen, an 8 mL hydrogenation vial was charged with [Ir(COD)Cl]2 (3.36 mg, 0.5 mmol%), the aforementioned ligand (1.02 mol%), and anhydrous tetrahydrofuran (1 mL). The mixture was stirred at 20-30°C for 0.5-1.0 h to form a yellow clear solution. Potassium tert-butoxide (2.8 mg, 2.5 mol%), acetophenone (120 mg, 1 mmol), and anhydrous tetrahydrofuran (3 mL) were then added to the reaction solution. The reaction mixture was then placed in a 250 mL hydrogenation kettle. The atmosphere was replaced with hydrogen four times, then filled with hydrogen at 5.0 MPa. The reaction was continued at 20-30°C for 48 h. After completion of the reaction, the chiral purity of the reaction solution was determined by HPLC.

[0038] The liquid phase conditions are: Column: OD-H; Mobile phase: n-hexane / isopropanol = 95 / 5, flow rate: 1.0 mL / min, isocratic elution; Detection wavelength: 210 nm; Retention time: 7.46 min ( S ), 9.02 min ( R ).

[0039] The screening results of some of the above ligands are shown in the following table: Serial number ligand Conversion rate (%) (%) 1 <h2 style=";text-align:left;direction:ltr"><![CDATA[ <h2 style=";text-align:left;direction:ltr"> (S <h2 style=";text-align:left;direction:ltr"> c <h2 style=";text-align:left;direction:ltr"> ,S <h2 style=";text-align:left;direction:ltr"> ax <h2 style=";text-align:left;direction:ltr"> ,R <h2 style=";text-align:left;direction:ltr"> Fc <h2 style=";text-align:left;direction:ltr"> ) <h2 style=";text-align:left;direction:ltr"> -L9]]><h2 style=";text-align:left;direction:ltr"> 64 72 2 <h2 style=";text-align:left;direction:ltr"><![CDATA[ <h2 style=";text-align:left;direction:ltr"> (S <h2 style=";text-align:left;direction:ltr"> c <h2 style=";text-align:left;direction:ltr"> ,S <h2 style=";text-align:left;direction:ltr"> ax <h2 style=";text-align:left;direction:ltr"> ,R <h2 style=";text-align:left;direction:ltr"> Fc <h2 style=";text-align:left;direction:ltr"> ) <h2 style=";text-align:left;direction:ltr"> -L2]]><h2 style=";text-align:left;direction:ltr"> 75 93 Although the present invention has been fully described in conjunction with the specific embodiments, it should be noted that various changes and modifications will be apparent to those skilled in the art. Such changes and modifications will be understood to be included within the scope of the invention as defined by the appended claims.

Claims

1. A chiral ferrocene-bridged binaphthyl skeleton phosphine ligand, characterized in that: The structural formula is: ， in: Ar in the chiral ferrocene-bridged binaphthyl skeleton phosphine ligand shown in formula I-IV is an aryl group or a substituted aryl group; R in Formula I-IV 1 One independently selected from hydrogen, aryl, alkyl, fluorine, chlorine, bromine, iodine, and alkoxy; R in Formula I-IV 2 Independently selected from one of NH2, NHMe, NMe2, NHAc, NHCOAr, NHSO2Me, NHSO2CF3, and NHSO2Ar, wherein Ar is an aryl group or a substituted aryl group.

2. The chiral ferrocene-bridged binaphthyl skeleton phosphine ligand according to claim 1, characterized in that: Ar in the chiral ferrocenium-bridged binaphthyl skeleton phosphine ligand represented by formula I-IV is phenyl.

3. The chiral ferrocene-bridged binaphthyl skeleton phosphine ligand according to claim 1, characterized in that: R in the formula I-IV 1 For hydrogen.

4. The chiral ferrocene-bridged binaphthyl skeleton phosphine ligand according to claim 1, characterized in that: R in the formula I-IV 2 It is NH2, NMe2, NHSO2Ar, wherein Ar is a substituted aryl group.

5. The chiral ferrocene-bridged binaphthyl skeleton phosphine ligand according to any one of claims 1 to 4, characterized in that: The structural formula is: ， ， 。 6. A method for preparing a chiral ferrocene-bridged binaphthyl skeleton phosphine ligand of formula III, characterized in that: The reaction formula is as follows: ， wherein Ar is an aryl group or a substituted aryl group; R 1 One independently selected from hydrogen, aryl, alkyl, fluorine, chlorine, bromine, iodine, and alkoxy; R 2 Independently selected from one of NH2, NHMe, NMe2, NHAc, NHCOAr, NHSO2Me, NHSO2CF3, and NHSO2Ar, wherein Ar is an aryl group or a substituted aryl group.

7. The method for preparing the chiral ferrocene-bridged binaphthyl skeleton phosphine ligand of formula III according to claim 6, characterized in that: described (S) -DI-NH2 and (S c ,R Fc ) The solvent for the -1 addition reaction is an organic solvent.

8. The method for preparing the chiral ferrocene-bridged binaphthyl skeleton phosphine ligand of formula III according to claim 6, characterized in that: described (S) -DI-NH2 and (S c ,R Fc ) The temperature of the -1 addition reaction is 50~70℃.

9. A catalyst for asymmetric hydrogenation reaction, characterized in that: It is prepared from a novel chiral ferrocenyl-bridged binaphthyl skeleton phosphine ligand and a transition metal and its salt.

10. The catalyst according to claim 9, characterized in that The transition metal is one of ruthenium, rhodium, palladium, iridium, iron, cobalt, nickel, copper, scandium, titanium, chromium, manganese, rhenium, osmium and platinum.

11. The catalyst according to claim 9, characterized in that The transition metal salt is a trivalent ruthenium salt, a bisphosphine ruthenium hydrogen complex, a bisphosphine divalent ruthenium complex, a bisphosphine diaryl divalent ruthenium complex, a disubstituted aryl divalent ruthenium complex, a bisphosphine disubstituted carboxyl divalent ruthenium complex, a bisphosphine bis(methylallyl)ruthenium complex, a substituted aryl tris(triphenylphosphine)ruthenium complex, (1,5-cyclopentadiene)(1,3,5-cyclooctatriene)ruthenium, (1,5 -cyclopentadiene)(1,3,5-cyclooctatriene) ruthenium salt, p-cymene divalent ruthenium complex, (1,5-cyclooctadiene) ruthenium chloride polymer, disubstituted arylbisphosphine ruthenium salt complex, dichloroaryl ruthenium complex, bis(methylallyl)(1,5-cyclooctadiene) ruthenium, biscarbonyl dichloride rhodium, bis-norbornadiene rhodium tetrafluoroborate, norbornadiene rhodium chloride dimer, (1,5-cyclo One of the following: (1,5-cyclooctadiene) rhodium chloride dimer, (1,5-cyclooctadiene) rhodium salt, dicarbonyl acetylacetonate rhodium, acetylacetonate di(ethylene) rhodium, bis(ethylene) rhodium chloride dimer, tris(triphenylphosphine) rhodium chloride, divalent palladium salt, tetrakis(triphenylphosphine) palladium, allyl palladium chloride, trivalent iridium salt, bis-norbornadiene iridium chloride dimer, (1,5-cyclooctadiene) iridium chloride, (1,5-cyclooctadiene) iridium salt, divalent iron salt, trivalent iron salt, nickel(II) acetylacetonate, divalent nickel salt, allyl nickel dimer, bis-(1,5-cyclooctadiene) nickel, monovalent copper salt, divalent copper salt, molybdenum acetylacetonate, divalent scandium salt, tetraisopropyl titanate, divalent chromium salt, trivalent chromium salt, pentacarbonyl manganese bromide, dimanganese decacarbonyl, divalent manganese salt, manganese(II) acetylacetonate, and methylrhenium trioxide.

12. Use of the chiral ferrocenium-bridged binaphthyl skeleton phosphine ligand according to claim 1 in the asymmetric hydrogenation of prochiral ketone compounds to synthesize chiral alcohols.

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