Process for the preparation of planar chiral aryl substituted ferrocenyl monophosphine ligands

Abstract

The application discloses a preparation method of an aryl-substituted ferrocene monophosphine ligand containing a planar chirality, and comprises the following steps: taking a compound of formula 1 as a raw material, taking divalent palladium as a catalyst, and controlling a reaction temperature to be 100-150 DEG C under the protection of an inert gas and in the participation of an alkali and a chiral ligand, so that the raw material and an aromatic halide are subjected to carbon-hydrogen activation reaction catalyzed by the catalyst to prepare the aryl-substituted ferrocene monophosphine ligand. The ligand has high efficiency and excellent performance in transition metal catalysis, the method has not been reported in the prior art, and raw materials are cheap and easy to obtain; unit operation is simple, equipment requirement is low, and the method is suitable for quickly constructing a novel planar chiral monophosphine ligand library.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of chemical synthesis, and particularly relates to a preparation method of a novel aryl-substituted ferrocene monophosphine ligand containing planar chirality. BACKGROUND

[0002] Transition metal catalyzed reactions are closely related to the development of ligands. Chiral phosphine ligands are the most widely used ligands in the field of cross-coupling, and are increasingly valued by synthetic chemists. A series of planar chiral ferrocene ligands have been synthesized, and representative ligands include Josiphos, Walphos, Bophoz, Taniaphos and Xyliphos. Among them, 1,2-disubstituted bidentate chiral ferrocene ligands are the most common, such as P,P-ligands, P,N-ligands, P,S-ligands, P,O-ligands and N,O-ligands. Among them, bidentate P,P-ligands are widely used in asymmetric catalysis. However, the exploration of monodentate P-ligands with planar chirality is relatively less. In addition, the planar chiral ferrocene phosphine ligands reported so far mainly focus on bidentate phosphine ligands, which combine central chirality and planar chirality. However, the synthesis of such ligands requires chiral starting materials, which affects the development and application of such ligands. Therefore, it is very attractive to develop a method for rapidly constructing chiral phosphine ligands containing planar chirality, and it is expected that such ligands will have high efficiency and excellent performance in transition metal catalysis. SUMMARY

[0003] In view of the above problems, the present application provides a preparation method of a novel aryl-substituted ferrocene monophosphine ligand containing planar chirality. The ligand has high efficiency and excellent performance in transition metal catalysis. The method has simple steps and can construct chiral aryl-substituted monophosphine ligands in one step, and is suitable for rapidly constructing a novel planar chiral ferrocene monophosphine ligand library.

[0004] The technical solution adopted by the present application to solve the technical problem is as follows:

[0005] The preparation method of the aryl-substituted ferrocene monophosphine ligand containing planar chirality comprises the following steps:

[0006] A compound of formula 1 is used as a raw material, divalent palladium is used as a catalyst, and the reaction is carried out in an organic solution under the protection of an inert gas in the presence of a base and a chiral ligand. The reaction temperature is controlled at 100-150 DEG C. The raw material and aromatic halide are subjected to carbon-hydrogen activation reaction catalyzed by the catalyst to prepare an aryl-substituted ferrocene monophosphine ligand. The structural formula of the aryl-substituted ferrocene monophosphine ligand is shown in formula 2.

[0007]

[0008] wherein R 1 is independently selected from phenyl, cyclohexyl or isopropyl; R 2 is selected from a hydrogen atom, phenyl or p-methoxyphenyl; is a poly-, mono- or unsubstituted benzene, biphenyl, naphthalene, phenanthrene, pyrene, pyridine, indazole or quinoline.

[0009] Preferably, the substituents in are independently selected from alkyl, alkoxy, phenoxy, alkylthio, alkylsilyl, halogen, haloalkyl, haloalkoxy, ester, acyl, sulfone or unsaturated hydrocarbon.

[0010] Preferably, the aromatic halide is

[0011] Preferably, the catalyst is one of palladium acetate, tris(dibenzylideneacetone)dipalladium, allylpalladium chloride dimer or 1,3-bis-(2,6-diisopropylphenyl)-imidazolyl-2-ylidene-(allyl)palladium; preferably the catalyst is 1,3-bis-(2,6-diisopropylphenyl)-imidazolyl-2-ylidene-(allyl)palladium.

[0012] Preferably, the chiral ligand is one of R-(+)-1,1'-binaphthalene-2,2'-diphenylphosphine, (S)-1-(diphenylphosphino)-2-[(S)-4-tert-butyl-oxazolidin-2-yl]ferrocene, (S)-(+)-(3,5-dioxa-4-phospha-cyclohept-2,1-A;3,4-A' di-naphthalenyl)-5H-dibenzo[B,F]azepine, (R)-(+)-(3,5-dioxa-4-phospha-cyclohept-2,1-A;3,4-A' di-naphthalenyl)-dimethylamine, N-dimethyl-[(R)-1,1'-spirobiindane-7,7'-diyl]phosphoramidite or (3AR,8AR)-(-)-(2,2-dimethyl-4,4,8,8-tetraphenyl-tetrahydro-[1,3]dioxolo[4,5-E][1,3,2]dioxaphos-6-yl)dimethylamine; preferably the chiral ligand is (R)-(-)-(3,5-dioxa-4-phospha-cyclohept-2,1-A;3,4-A' di-naphthalenyl)-dimethylamine.

[0013] Preferably, the molar ratio of catalyst, chiral ligand, starting material and aromatic halide is 5-10%: 11-22%: 1: 1-2.

[0014] Preferably, the organic solvent is one or a mixture of more than one of toluene, tetrahydrofuran or 1,4-dioxane; preferably the organic solvent is tetrahydrofuran.

[0015] Preferably, the base is one of potassium phosphate, cesium carbonate, lithium tert-butoxide or cesium pivalate; preferably the base is cesium carbonate.

[0016] Preferably, the base is in a molar ratio of 1-2:1 to the raw material; preferably the molar ratio is 1.5:1.

[0017] Preferably, the inert gas is argon or nitrogen.

[0018] Preferably, the reaction time is 48-72 hours.

[0019] The application also provides the aryl-substituted ferrocenyl monophosphine ligand with planar chirality prepared by the above method.

[0020] The partial chemical reaction equations of the above preparation method are as follows:

[0021]

[0022] wherein, R 1 , R 2 and The definitions of R, R and R are the same as above. L* is a chiral ligand.

[0023] The application provides a new synthetic route of aryl-substituted ferrocenyl monophosphine ligand with planar chirality, which has high efficiency and excellent performance in transition metal catalysis.

[0024] The raw materials of the synthetic route of the application are cheap and easy to obtain, the unit operation is simple, the equipment requirement is low, and the synthetic route is suitable for quickly constructing a new library of ferrocenyl monophosphine ligand with planar chirality.

[0025] Additional aspects and advantages of the application will be in part apparent and in part pointed out hereinafter. DETAILED DESCRIPTION

[0026] The following is a specific embodiment of the application, which further describes the technical solutions of the application, but the application is not limited to this embodiment.

[0027] Example 1

[0028] Synthesis of (1R)-1-[2-(diphenylphosphino)phenyl]-2-[4-methoxyphenyl]ferrocene:

[0029] A 25 mL Schlenk tube was oven dried at 630 °C for three times with a high temperature oven gun. After cooling, [2-(diphenylphosphino)phenyl]ferrocene (1.0 equiv, 0.10 mmol), 4-bromoanisole (2.0 equiv, 0.2 mmol, 26 μL), 1,3-bis-(2,6-diisopropylphenyl)-imidazolyl-2-ylidene-(allyl) palladium chloride (5% of the raw material molar, 0.005 mmol, 2.9 mg), (R)-(3,5-dioxo-4-phospha-cycloheptyl[2,1-A,3,4-A']binaphthyl)dimethylamine (11% of the raw material molar, 0.011 mmol, 4.0 mg), cesium carbonate (1.5 equiv, 0.15 mmol, 48.9 mg) were dissolved in super dry tetrahydrofuran (1.0 mL) in a glove box. The mixture was stirred at 100 °C for 48 h under argon atmosphere. After the reaction was completed, the mixture was cooled to room temperature and the solvent was removed by rotary evaporation under reduced pressure. The product was isolated by column chromatography on 300-400 mesh silica gel using petroleum ether: ethyl acetate = 100: 1 as eluent. After drying in vacuum, 36.0 mg of product was obtained with a yield of 66% and an enantiomeric excess of 95%. 1 HNMR (400 MHz, CDC13) δ 8.03 (dd, J = 7.2, 4.4 Hz, 1H), 7.34 (t, J = 7.6 Hz, 1H), 7.29-7.28 (m, 3H), 7.21-7.12 (m, 6H), 7.10 (d, J = 8.8 Hz, 2H), 6.94 (dd, J = 7.2, 3.2 Hz, 1H), 6.89 (t, J = 7.2 Hz, 2H), 6.64 (d, J = 8.8 Hz, 2H), 4.55 (s, 1H), 4.26 (t, J = 2.4 Hz, 1H), 4.21 (s, 1H), 4.16 (s, 5H), 3.76 (s, 3H). 13 C NMR (101 MHz, CDC13) δ 157.9, 143.3 (d, J = 29.1 Hz), 138.5 (d, J = 14.1 Hz), 138.0 (dd, J = 23.1, 13.2 Hz), 134.0, 133.71, 133.69 (dd, J = 19.7, 3.2 Hz), 130.7 (d, J = 1.1 Hz), 130.2, 128.4, 128.3 (d, J = 12.1 Hz), 128.2 (d, J = 21.1 Hz), 127.1, 113.2, 89.3 (d, J = 9.9 Hz), 88.3 (d, J = 2.4 Hz), 72.5 (t, J = 7.6 Hz), 70.5 (d, J = 3.3 Hz), 68.5 (d, J = 3.6 Hz), 66.4 (d, J = 3.6 Hz), 55.3 (d, J = 5.4 Hz). 31P NMR (162 MHz, CDC13) δ -13.92.

[0030] Example 2

[0031] Synthesis of (1R)-1-[2-(diphenylphosphino)phenyl]-2-phenyldiphenylphosphinoferrocene:

[0032] A 25 mL Schlenk tube was oven dried at 630 °C for three times with a high temperature oven gun. After cooling, [2-(diphenylphosphino)phenyl]diphenylphosphinoferrocene (1.0 eq, 0.10 mmol), bromobenzene (2.0 eq, 0.2 mmol, 21 μL), 1,3-bis-(2,6-diisopropylphenyl)-imidazolyl-2-ylidene-(allyl)palladium (5% of the raw material molar, 0.005 mmol, 2.9 mg), (R)-(3,5-dioxo-4-phospha-cycloheptyl[2,1-A,3,4-A']dinaphthalenyl)dimethylamine (11% of the raw material molar, 0.011 mmol, 4.0 mg), cesium carbonate (1.5 eq, 0.15 mmol, 48.9 mg) were dissolved in super dry tetrahydrofuran (1.0 mL) in a glove box. The mixture was stirred at 100 °C for 48 h under argon atmosphere. After the reaction was completed, the mixture was cooled to room temperature, and the solvent was removed by rotary evaporation under reduced pressure. The product was isolated by column chromatography on 300-400 mesh silica gel using petroleum ether: ethyl acetate = 500: 1 as eluent. After drying under vacuum, 26.6 mg of product was obtained with a yield of 51% and an enantiomeric excess of 89%. 1 H NMR (400 MHz, CDC13) δ 8.01 (dd, J = 7.2, 4.4 Hz, 1H), 7.35 - 7.29 (m, 4H), 7.22 - 7.08 (m, 11H), 6.93 (dd, J = 7.6, 3.2 Hz, 1H), 6.87 (t, J = 7.2 Hz, 2H), 4.60 (s, 1H), 4.28 (t, J = 2.0 Hz, 1H), 4.23 (s, 1H), 4.17 (s, 5H). 13 C NMR (126 MHz, CDC13) δ 143.1 (d, J = 2.9 Hz), 138.7, 138.6 (d, J = 14.4 Hz), 137.9 (dd, J = 13.4, 4.6 Hz), 133.9, 133.72 (dd, J = 19.5, 2.1 Hz), 133.71 (d, J = 5.1 Hz), 129.1, 128.4 (d, J = 10.9 Hz), 128.3 (d, J = 21.1 Hz), 128.2, 127.7, 127.1, 125.8, 89.4 (d, J = 9.8 Hz), 88.1 (d, J = 1.9 Hz), 72.9 (d, J = 7.9 Hz), 70.6, 68.9, 66.7. 31PNMR (202 MHz, CDCI3) δ -13.7.

[0033] Example 3

[0034] Synthesis of (1R)-1-[2-(diphenylphosphino)phenyl]-2-[4-methylphenyl]ferrocene:

[0035] A 25 mL Schlenk tube was oven dried at 630 °C three times with a high temperature oven gun. After cooling, [2-(diphenylphosphino)phenyl]ferrocene (1.0 eq, 0.10 mmol), 4-bromotoluene (2.0 eq, 0.2 mmol, 25 μL), 1,3-bis-(2,6-diisopropylphenyl)-imidazolyl-2-ylidene-(allyl)palladium (5% of the starting material, 0.005 mmol, 2.9 mg), (R)-(3,5-dioxo-4-phospha-cycloheptyl[2,1-A,3,4-A']dinaphthalenyl)dimethylamine (11% of the starting material, 0.011 mmol, 4.0 mg), cesium carbonate (1.5 eq, 0.15 mmol, 48.9 mg) were dissolved in super dry tetrahydrofuran (1.0 mL) in a glove box. The mixture was stirred at 100 °C under argon atmosphere for 48 hours. After the reaction was completed, the mixture was cooled to room temperature and the solvent was removed by rotary evaporation under reduced pressure. The product was isolated by column chromatography on 300-400 mesh silica gel using petroleum ether: ethyl acetate = 500:1 as eluent. After drying under vacuum, 23.1 mg of product was obtained in 43% yield with 93% enantiomeric excess. 1 HNMR (400 MHz, CDC13) δ 8.02 (dd, J = 7.6, 4.8 Hz, 1H), 7.36-7.29 (m, 4H), 7.21-7.12 (m, 6H), 7.08 (d, J = 8.0 Hz, 2H), 6.96-6.86 (m, 5H), 4.58 (s, 1H), 4.27 (t, J = 2.4 Hz, 1H), 4.24 (s, 1H), 4.17 (s, 5H), 2.28 (s, 3H). 13C NMR (101 MHz, CDC13) δ 143.3 (d, J = 29.0 Hz), 138.5 (d, J = 14.1 Hz), 138.0 (dd, J = 15.1, 13.3 Hz), 135.5 (d, J = 1.2 Hz), 135.3, 134.0 (d, J = 1.2 Hz), 133.8 (d, J = 3.6 Hz), 133.7, 133.6 (d, J = 2.9 Hz), 129.1, 128.3 (dd, J = 22.3, 6.5 Hz), 128.2 (dd, J = 20.2, 2.8 Hz), 127.1, 89.4 (d, J = 9.8 Hz), 88.3 (d, J = 2.2 Hz). 72.7 (d, J = 7.9 Hz), 70.6, 68.8, 66.6, 21.2. 31 PNMR (162 MHz, CDC13) δ -14.00.

[0036] Example 4

[0037] Synthesis of (1R)-1-[2-(diphenylphosphino)phenyl]-2-[3-methylphenyl]ferrocene:

[0038] A 25 mL Schlenk tube was oven dried at 630 °C using a high temperature oven gun for three times. After cooling, [2-(diphenylphosphino)phenyl]ferrocene (1.0 eq, 0.10 mmol), 3-bromotoluene (2.0 eq, 0.2 mmol, 24 μL), 1,3-bis-(2,6-diisopropylphenyl)-imidazolyl-2-ylidene-(allyl) palladium chloride (5% of the raw material molar, 0.005 mmol, 2.9 mg), (R)-(3,5-dioxo-4-phospha-cycloheptyl[2,1-A,3,4-A']dinaphthalenyl)dimethylamine (11% of the raw material molar, 0.011 mmol, 4.0 mg), cesium carbonate (1.5 eq, 0.15 mmol, 48.9 mg) were dissolved in super dry tetrahydrofuran (1.0 mL) in a glove box. The mixture was stirred at 100 °C for 48 hours under argon atmosphere. After the reaction was completed, the mixture was cooled to room temperature and the solvent was removed by rotary evaporation under reduced pressure. The product was isolated by column chromatography on 300-400 mesh silica gel using petroleum ether: ethyl acetate = 500: 1 as eluent. The product was dried under vacuum to give 25.7 mg in 48% yield with 92% enantiomeric excess. 1 H NMR (500 MHz, CDC13) δ 8.06-7.97 (m, 1H), 7.32 (m, 7.6 Hz, 4H), 7.16 (m, 6H), 6.97 (m, 4H), 6.89 (m, 3H), 4.58 (d, J = 1.5 Hz, 1H), 4.29 (d, J = 2.5 Hz, 1H), 4.26 (s, 1H), 4.18 (s, 5H), 2.19 (s, 3H).13 C NMR (126 MHz, CDC13) δ 143.3 (d, J = 29.1 Hz), 138.6 (d, J = 14.1 Hz), 138.5, 138.0 (dd, J = 26.3, 13.3 Hz), 137.0, 133.9 (d, J = 22.0 Hz), 133.7 (d, J = 20.2 Hz), 129.9, 128.4 (d, J = 6.5 Hz), 128.3, 128.1, 128.1 (d, J = 6.5 Hz), 127.5, 127.1, 126.6, 126.4, 89.5 (d, J = 10.2 Hz), 88.3 (d, J = 2.1 Hz), 72.8 (d, J = 8.1 Hz), 70.6, 68.9, 66.6, 21.5. 31 P NMR (202 MHz, CDC13) δ -13.98.

[0039] Example 5

[0040] Synthesis of (1R)-1-[2-(diphenylphosphino)phenyl]-2-[3,5-dimethylphenyl]ferrocene:

[0041] A 25 mL Schlenk tube was oven dried at 630 °C three times with a high temperature oven gun, after waiting for cooling, [2-(diphenylphosphino)phenyl]ferrocene (1.0 eq, 0.10 mmol), 3,5-dimethylbromobenzene (2.0 eq, 0.2 mmol, 27 μL), 1,3-bis-(2,6-diisopropylphenyl)-imidazolyl-2-ylidene-(allyl) palladium chloride (5% of the raw material molar, 0.005 mmol, 2.9 mg), (R)-(3,5-dioxo-4-phospha-cycloheptyl[2,1-A,3,4-A']dinaphthalenyl)dimethylamine (11% of the raw material molar, 0.011 mmol, 4.0 mg), cesium carbonate (1.5 eq, 0.15 mmol, 48.9 mg) were dissolved in super dry tetrahydrofuran (1.0 mL) in a glove box. The mixture was stirred at 100 °C for 48 hours under argon atmosphere. After the reaction was completed, it was cooled to room temperature, and then the solvent was removed by rotary evaporation under reduced pressure. The product was obtained by silica gel column chromatography (300-400 mesh) using petroleum ether: ethyl acetate = 500:1 as eluent, and dried under vacuum. The yield was 34.1 mg, 62%, with an enantiomeric excess of 90%. 1HNMR (500 MHz, CDC13) δ 8.00 (ddd, J = 7.5, 4.5, 1.0 Hz, 1H), 7.34 - 7.28 (m, 4H), 7.21 - 7.12 (m, 6H), 6.96 (ddd, J = 8.0, 4.0, 1.0 Hz, 1H), 6.93 - 6.90 (m, 2H), 6.76 (s, 2H), 6.70 (s, 1H), 4.57 (t, J = 2.0 Hz, 1H), 4.29 (d, J = 1.5 Hz, 2H), 4.18 (s, 5H), 2.14 (s, 6H). 13 C NMR (126 MHz, CDC13) δ 143.4 (d, J = 29.1 Hz), 138.4 (dd, J = 25.8, 13.8 Hz), 137.8 (d, J = 13.3 Hz), 136.8, 134.0, 133.8 (d, J = 5.3 Hz), 133.7 (dd, J = 20.0, 2.3 Hz), 128.4 (d, J = 6.3 Hz), 128.2, 128.12 (d, J = 2.8 Hz), 128.05, 127.6, 127.2, 127.0, 89.4 (d, J = 10.0 Hz), 88.5 (d, J = 1.5 Hz), 72.7 (d, J = 8.5 Hz), 70.6, 69.0, 66.5, 21.4. 31 P NMR (202 MHz, CDC13) δ -14.19.

[0042] Example 6

[0043] Synthesis of (1R)-1-[2-(diphenylphosphino)phenyl]-2-[4- ethylphenyl]ferrocene:

[0044] A 25 mL Schlenk tube was oven dried at 630 °C three times with a high temperature oven gun, and after allowing to cool, [2-(diphenylphosphino)phenyl]ferrocene (1.0 equiv, 0.10 mmol), 4-bromoethylbenzene (2.0 equiv, 0.2 mmol, 28 μί), 1,3-bis-(2,6-diisopropylphenyl)-imidazolyl-2-ylidene-(allyl)palladium (5% of the moles of starting material, 0.005 mmol, 2.9 mg), R-(+)-1,1'-binaphthalene-2,2'-bisdiphenylphosphine (11% of the moles of starting material, 0.011 mmol, 4.0 mg), cesium carbonate (1.5 equiv, 0.15 mmol, 48.9 mg) were dissolved in super-dry tetrahydrofuran (1.0 mL) in a glovebox. The mixture was stirred at 100 °C under an argon atmosphere for 48 h. After the reaction was complete, the mixture was cooled to room temperature and the solvent was removed by rotary evaporation under reduced pressure. The product was isolated by chromatography on a 300-400 mesh silica gel column using petroleum ether: ethyl acetate = 500: 1 as eluent. The product was dried under vacuum to give 31.4 mg, 57% yield, with an enantiomeric excess of 91%. 1 H NMR (500 MHz, CDC13) δ 8.04 (dd, J = 7.5, 4.0 Hz, 1H), 7.35 (td, J = 7.5, 1.5 Hz, 1H), 7.31-7.26 (m, 3H), 7.23-7.08 (m, 8H), 6.94 (dd, J = 9.5, 6.5 Hz, 3H), 6.85 (td, J = 7.0, 1.5 Hz, 2H), 4.58 (t, J = 2.5 Hz, 1H), 4.27 (t, J = 2.5 Hz, 1H), 4.22 (dd, J = 2.5, 1.5 Hz, 1H), 4.18 (s, 5H), 2.59 (q, J = 7.5 Hz, 2H), 1.24 (t, J = 7.5 Hz, 3H). 13 C NMR (126 MHz, CDC13) δ 143.4 (d, J = 28.5 Hz), 141.7, 138.6 (d, J = 14.5 Hz), 138.0 (dd, J = 13.5, 5.5 Hz), 135.8, 134.0, 133.7 (d, J = 4.5 Hz), 133.7, 133.6 (d, J = 4.5 Hz), 128.3 (t, J = 6.5 Hz), 128.2, 128.1 (d, J = 4.0 Hz), 127.2, 127.1, 89.4 (d, J = 10.0 Hz), 88.3 (d, J = 3.8 Hz), 72.7 (d, J = 7.5 Hz), 70.6, 68.6, 66.6, 28.6, 15.5. 31 PNMR (202 MHz, CDC13) δ -13.94.

[0045] Example 7

[0046] Synthesis of (1R)-1-[2-(diphenylphosphino)phenyl]-2-[4-n-butylphenyl]ferrocene:

[0047] A 25 mL Schlenk tube was oven dried at 630 °C three times with a high temperature oven gun. After cooling, [2-(diphenylphosphino)phenyl]ferrocene (1.0 equiv, 0.10 mmol), p-bromobutylbenzene (2.0 equiv, 0.2 mmol, 35 μL), allylpalladium chloride dimer (5% of the moles of starting material, 0.005 mmol, 2.9 mg), (R)-(3,5-dioxo-4-phospha-cycloheptyl[2,1-A,3,4-A']binaphthyl)dimethylamine (11% of the moles of starting material, 0.011 mmol, 4.0 mg), cesium carbonate (1.5 equiv, 0.15 mmol, 48.9 mg) were dissolved in super dry tetrahydrofuran (1.0 mL) in a glove box. The mixture was stirred at 100 °C under argon atmosphere for 48 h. After the reaction was completed, the mixture was cooled to room temperature and the solvent was removed by rotary evaporation under reduced pressure. The product was isolated by column chromatography on 300-400 mesh silica gel using petroleum ether: ethyl acetate = 500:1 as eluent. After drying under vacuum, 31.2 mg of product was obtained in 54% yield with an enantiomeric excess of 94%. 1 HNMR (400 MHz, CDC13) δ 8.03 (dd, J = 6.8, 4.4 Hz, 1H), 7.34 (t, J = 7.6 Hz, 1H), 7.30-7.27 (m, 3H), 7.22-7.08 (m, 8H), 6.92 (d, J = 8.0 Hz, 3H), 6.85 (t, J = 6.8 Hz, 2H), 4.58 (s, 1H), 4.26 (t, J = 2.4 Hz, 1H), 4.20 (s, 1H), 4.17 (s, 5H), 2.54 (t, J = 7.6 Hz, 2H), 1.65-1.58 (m, 2H), 1.43-1.33 (m, 2H), 0.95 (t, J = 7.6 Hz, 3H). 13C NMR (101 MHz, CDC13) δ 143.2 (d, J = 29.2 Hz), 140.3, 138.5 (d, J = 14.3 Hz), 137.9 (t, J = 13.7 Hz), 135.7 (d, J = 1.4 Hz), 133.8 (d, J = 1.3 Hz), 133.58 (d, J = 5.2 Hz), 133.55 (dd, J = 19.8, 5.9 Hz), 128.9, 128.2, 128.13 (dd, J = 19.7, 9.4 Hz), 128.0, 127.6, 127.0, 89.2 (d, J = 10.0 Hz), 88.2 (d, J = 2.5 Hz), 72.6 (d, J = 7.6 Hz), 70.5, 68.5, 66.4, 35.4, 33.6, 22.5 14.1. 31 PNMR (162 MHz, CDC13) δ -13.88.

[0048] Example 8

[0049] Synthesis of (1R)-1-[2-(diphenylphosphino)phenyl]-2-[4-n-pentylphenyl]ferrocene:

[0050] A 25 mL Schlenk tube was oven dried at 630 °C three times with a high temperature oven gun. After allowing to cool, [2-(diphenylphosphino)phenyl]ferrocene (1.0 eq, 0.10 mmol), p-pentylbromobenzene (2.0 eq, 0.2 mmol, 36 μL), 1,3-bis-(2,6-diisopropylphenyl)-imidazolyl-2-ylidene-(allyl)palladium (5% of the moles of starting material, 0.005 mmol, 2.9 mg), (R)-(3,5-dioxo-4-phospha-cycloheptyl[2,1-A,3,4-A']dinaphthalenyl)dimethylamine (11% of the moles of starting material, 0.011 mmol, 4.0 mg), cesium carbonate (1.5 eq, 0.15 mmol, 48.9 mg) were dissolved in super-dry tetrahydrofuran (1.0 mL) in a glove box. The mixture was stirred at 100 °C under an argon atmosphere for 48 h. After the reaction was complete, the mixture was cooled to room temperature and the solvent was removed by rotary evaporation under reduced pressure. The product was isolated by chromatography on a 300-400 mesh silica gel column using petroleum ether: ethyl acetate = 500:1 as eluent. The product was dried under vacuum to give 32.6 mg, 55% yield, 95% enantiomeric excess. 1HNMR (500 MHz, CDC13) δ 8.08 - 7.99 (m, 1H), 7.34 (m, 1H), 7.31 - 7.27 (m, 3H), 7.21 - 7.08 (m, 8H), 6.92 (d, J = 8.0 Hz, 3H), 6.85 (m, 2H), 4.57 (dd, J = 2.5, 1.5 Hz, 1H), 4.25 (t, J = 2.5 Hz, 1H), 4.20 (m, 1H), 4.17 (s, 5H), 2.53 (t, J = 7.5 Hz, 2H), 1.61 (m, 2H), 1.40 - 1.33 (m, 4H), 0.92 (t, J = 7.0 Hz, 3H). 13 C NMR (126 MHz, CDC13) δ 143.2 (d, J = 29.1 Hz), 140.3, 138.5 (d, J = 14.3 Hz), 137.9 (t, J = 13.8 Hz), 135.8 (d, J = 1.4 Hz), 133.8 (d, J = 1.3 Hz), 133.58 (d, J = 5.3 Hz), 133.57 (dd, J = 19.8, 7.1 Hz), 128.9, 128.2 (d, J = 1.6 Hz), 128.1 (dd, J = 24.7, 10.6 Hz), 128.0, 127.6, 127.0, 89.2 (d, J = 12.1 Hz), 88.2 (d, J = 2.4 Hz), 72.6 (d, J = 7.7 Hz), 70.5, 68.5, 66.4, 35.7, 31.7, 31.1, 22.6, 14.1. 31 P NMR (202 MHz, CDC13) δ -13.85.

[0051] Example 9

[0052] Synthesis of (1R)-1-[2-(diphenylphosphino)phenyl]-2-[4- isopropylphenyl]ferrocene:

[0053] A 25 mL Schlenk tube was oven dried at 630 °C for three times with a high temperature oven gun. After cooling, [2-(diphenylphosphino)phenyl]ferrocene (1.0 equiv, 0.10 mmol), 1-bromo-4- isopropylbenzene (2.0 equiv, 0.2 mmol, 31 μL), 1,3-bis-(2,6-diisopropylphenyl)-imidazolyl-2- ylidene-(allyl)palladium (5% of the raw material molar, 0.005 mmol, 2.9 mg), (S)-1- (diphenylphosphino)-2-[(S)-4-tert-butyl-oxazolidin-2-yl]ferrocene (11% of the raw material molar, 0.011 mmol, 4.0 mg), cesium carbonate (1.5 equiv, 0.15 mmol, 48.9 mg) were dissolved in super dry tetrahydrofuran (1.0 mL) in a glove box. The mixture was stirred at 100 °C for 48 h under argon atmosphere. After the reaction was completed, the mixture was cooled to room temperature and the solvent was removed by rotary evaporation under reduced pressure. The product was isolated by column chromatography on 300-400 mesh silica gel using petroleum ether: ethyl acetate = 500: 1 as eluent. The product was dried under vacuum to give 25.4 mg in 45% yield with 95% enantiomeric excess. 1 HNMR (500 MHz, CDC13) δ 8.04 (dd, J = 7.5, 4.0 Hz, 1H), 7.34 (t, J = 7.5 Hz, 1H), 7.29-7.26 (m, 3H), 7.21-7.08 (m, 8H), 6.96 (dd, J = 8.0, 2.5 Hz, 2H), 6.93-6.87 (m, 1H), 6.81 (dt, J = 10.0, 5.0 Hz, 2H), 4.57 (s, 1H), 4.24 (s, 1H), 4.19 (s, 1H), 4.16 (d, J = 2.5 Hz, 5H), 2.84 (hept, J = 7.0 Hz, 1H), 1.24 (d, J = 7.0 Hz, 6H). 13 C NMR (126 MHz, CDC13) δ 146.2, 143.2 (d, J = 29.1 Hz), 138.5 (d, J = 14.4 Hz), 137.9 (dd, J = 34.0, 14.0 Hz), 135.9, 133.8, 133.522 (dd, J = 19.7, 12.6 Hz), 133.519, 128.9, 128.2 (d, J = 4.8 Hz), 128.1 (dd, J = 23.6, 11.5 Hz), 128.0, 127.0, 125.6, 89.3 (d, J = 9.8 Hz), 88.2 (d, J = 2.6 Hz), 72.6 (d, J = 7.3 Hz), 70.5, 68.4, 66.5, 33.7, 24.0 (d, J = 8.8 Hz). 31 P NMR (202 MHz, CDC13) δ -13.92.

[0054] Example 10

[0055] Synthesis of (1R)-1-[2-(diphenylphosphino)phenyl]-2-[4-cyclohexylphenyl]ferrocene:

[0056] A 25 mL Schlenk tube was oven dried at 630 °C three times with a high temperature oven gun, after waiting for cooling, in the glove box [2-(diphenylphosphino)phenyl]ferrocene (1.0 eq, 0.10 mmol), 1-bromo-4-cyclohexylbenzene (2.0 eq, 0.2 mmol, 37 μL), 1,3-bis-(2,6-diisopropylphenyl)-imidazolyl-2-ylidene-(allyl) palladium chloride (5% of the raw material molar, 0.005 mmol, 2.9 mg), (R)-(3,5-dioxo-4-phospha-cycloheptyl[2,1-A,3,4-A']dinaphthalenyl)dimethylamine (11% of the raw material molar, 0.011 mmol, 4.0 mg), cesium carbonate (1.5 eq, 0.15 mmol, 48.9 mg) were dissolved in super dry tetrahydrofuran (1.0 mL). The mixture was stirred at 100 °C for 48 hours under argon atmosphere. After the reaction was completed, it was cooled to room temperature, and the solvent was removed by rotary evaporation under reduced pressure, and separated by 300-400 mesh silica gel column chromatography, eluted with petroleum ether: ethyl acetate = 500:1, and dried under vacuum to obtain 36.3 mg of product, with a yield of 60%, and an enantiomeric excess value of 96%. 1 HNMR (500 MHz, CDC13) δ 8.07 (dd, J = 7.0, 4.5 Hz, 1H), 7.37 (t, J = 7.5 Hz, 1H), 7.30 (d, J = 11.0 Hz, 3H), 7.24-7.11 (m, 8H), 6.98 (d, J = 8.0 Hz, 2H), 6.93 (dd, J = 7.0, 3.0 Hz, 1H), 6.84 (t, J = 7.0 Hz, 2H), 4.60 (s, 1H), 4.28 (s, 1H), 4.22 (s, 1H), 4.20 (s, 5H), 2.46 (s, 1H), 1.89 (d, J = 12.5 Hz, 4H), 1.78 (d, J = 12.0 Hz, 1H), 1.43 (t, J = 10.0 Hz, 4H), 1.29 (s, 1H). 13C NMR (126 MHz, CDC13) δ 145.46, 143.23 (d, J = 29.2 Hz), 138.53 (d, J = 14.4 Hz), 137.91 (dd, J = 34.8, 13.8 Hz), 135.85, 133.81, 133.55 (dd, J = 20.0, 11.2 Hz), 133.55, 128.90, 128.21 (d, J = 2.8 Hz), 128.11 (dd, J = 22.1, 11.1 Hz), 128.02, 127.00, 126.00, 89.29 (d, J = 9.8 Hz), 88.21 (d, J = 2.8 Hz), 72.61 (d, J = 7.4 Hz), 70.46, 68.42, 66.44, 44.21, 34.46 (d, J = 7.9 Hz), 26.98, 26.25. 31 PNMR (202 MHz, CDC13) δ -13.90.

[0057] Example 11

[0058] Synthesis of (1R)-1-[2-(diphenylphosphino)phenyl]-2-[4-tert-butylphenyl]ferrocene:

[0059] A 25 mL Schlenk tube was oven dried at 630 °C three times with a high temperature oven gun. After cooling, [2-(diphenylphosphino)phenyl]ferrocene (1.0 eq, 0.10 mmol), 4-tert-butylbromobenzene (2.0 eq, 0.2 mmol, 35 μL), 1,3-bis-(2,6-diisopropylphenyl)-imidazolyl-2-ylidene-(allyl) palladium chloride (5% of the starting material molar amount, 0.005 mmol, 2.9 mg), (R)-(3,5-dioxo-4-phospha-cycloheptyl[2,1-A,3,4-A']dinaphthalenyl)dimethylamine (11% of the starting material molar amount, 0.011 mmol, 4.0 mg), cesium carbonate (1.5 eq, 0.15 mmol, 48.9 mg) were dissolved in super dry tetrahydrofuran (1.0 mL) in a glove box. The mixture was stirred at 100 °C under argon atmosphere for 48 hours. After the reaction was completed, the mixture was cooled to room temperature and the solvent was removed by rotary evaporation under reduced pressure. The product was isolated by 300-400 mesh silica gel column chromatography using petroleum ether: ethyl acetate = 500:1 as eluent. After drying under vacuum, 31.0 mg of product was obtained with a yield of 54% and an enantiomeric excess of 93%. 1HNMR (400 MHz, CDC13) δ 8.06 (ddd, J = 7.6, 3.2, 2.4 Hz, 1H), 7.36 (td, J = 7.6, 1.2 Hz, 1H), 7.28 - 7.26 (m, 3H), 7.20 (td, J = 7.6, 1.2 Hz, 1H), 7.14 - 7.09 (m, 9H), 6.90 (ddd, J = 7.6, 4.0, 0.8 Hz, 1H), 6.82 - 6.78 (m, 2H), 4.58 (dd, J = 2.4, 1.6 Hz, 1H), 4.25 (t, J = 2.4 Hz, 1H), 4.19 - 4.17 (m, 6H), 1.31 (s, 9H). 13 C NMR (126 MHz, CDC13) δ 148.5, 143.4 (d, J = 29.1 Hz), 138.7 (d, J = 14.3 Hz), 138.0 (dd, J = 46.1, 13.8 Hz), 135.6, 133.9 (d, J = 1.1 Hz), 133.6 (dd, J = 19.8, 17.0 Hz), 128.7, 128.4, 128.3 (d, J = 4.6 Hz), 128.1 (d, J = 6.4 Hz), 128.1, 127.1, 124.6, 89.5 (d, J = 9.9 Hz), 88.1 (d, J = 2.8 Hz), 72.8 (d, J = 7.0 Hz), 70.6, 68.5, 66.6, 34.6, 31.5. 31 P NMR (162 MHz, CDC13) δ -13.97.

[0060] Example 12

[0061] Synthesis of (1R)-1-[2-(diphenylphosphino)phenyl]-2-[4-phenylphenyl]ferrocene:

[0062] A 25 mL Schlenk tube was oven dried at 630 °C three times with a hot gun, and after allowing to cool, [2-(diphenylphosphino)phenyl]ferrocene (1.0 equiv, 0.10 mmol), 4-bromobiphenyl (2.0 equiv, 0.2 mmol, 46.6 mg), l,3-bis-(2,6-diisopropylphenyl)-imidazolyl-2-ylidene-(allyl)palladium (5% of the moles of starting material, 0.005 mmol, 2.9 mg), (R)-(3,5-dioxo-4-phospha-cycloheptyl[2,l-A',3,4-A']dinaphthalenyl)dimethylamine (11% of the moles of starting material, 0.011 mmol, 4.0 mg), cesium carbonate (1.5 equiv, 0.15 mmol, 48.9 mg) were dissolved in super-dry tetrahydrofuran (1.0 mL) in a glove box. The mixture was stirred at 100 °C under an argon atmosphere for 48 hours. After the reaction was complete, the mixture was cooled to room temperature and the solvent was removed by rotary evaporation under reduced pressure. The product was isolated by chromatography on a 300-400 mesh silica gel column using petroleum ether: ethyl acetate = 500: 1 as eluent. The product was dried under vacuum to give 37.7 mg, 63% yield, with an enantiomeric excess of 90%. 1 HNMR (500 MHz, CDC13) δ 8.11 (ddd, J = 7.5, 6.0, 2.5 Hz, 1H), 7.60 (d, J = 7.5 Hz, 2H), 7.44 (t, J = 7.5 Hz, 2H), 7.39 (td, J = 7.5, 1.0 Hz, 1H), 7.37-7.33 (m, 3H), 7.29-7.28 (m, 3H), 7.27-7.26 (m, 2H), 7.23 (td, J = 7.5, 1.0 Hz, 1H), 7.17-7.13 (m, 3H), 7.10 (td, J = 7.0, 1.5 Hz, 2H), 6.97 (ddd, J = 7.5, 3.5, 0.5 Hz, 1H), 6.85 (td, J = 7.0, 1.5 Hz, 2H), 4.67 (t, J = 1.5 Hz, 1H), 4.33 (t, J = 2.5 Hz, 1H), 4.30-4.28 (m, 1H), 4.22 (s, 5H). 13C NMR (126 MHz, CDC13) δ 143.2 (d, J = 29.1 Hz), 141.1, 138.7 (d, J = 14.1 Hz), 138.4, 138.1 (d, J = 1.5 Hz), 137.9 (dd, J = 29.1, 13.4 Hz), 134.1 (d, J = 1.3 Hz), 133.640 (d, J = 19.9 Hz), 133.638 (d, J = 5.2 Hz), 129.4, 128.8, 128.5, 128.27, 128.26 (dd, J = 21.3, 6.5 Hz), 128.1, 127.2 (d, J = 21.2 Hz), 126.9, 126.4, 89.8 (d, J = 9.9 Hz), 87.5 (d, J = 2.6 Hz), 73.1 (d, J = 6.9 Hz), 70.7, 68.4, 66.9. 31 PNMR (202 MHz, CDC13) δ -13.97.

[0063] Example 13

[0064] Synthesis of (1R)-1-[2-(diphenylphosphino)phenyl]-2-[3-methoxyphenyl]ferrocene:

[0065] A 25 mL Schlenk tube was oven dried at 630 °C three times with a high temperature oven gun. After allowing to cool, [2-(diphenylphosphino)phenyl]ferrocene (1.0 equiv, 0.10 mmol), 3-bromophenyl methyl ether (2.0 equiv, 0.2 mmol, 28 μL), 1,3-bis-(2,6-diisopropylphenyl)-imidazolyl-2-ylidene-(allyl) palladium chloride (5% of the moles of starting material, 0.005 mmol, 2.9 mg), (R)-(3,5-dioxo-4-phospha-cycloheptyl[2,1-A,3,4-A']dinaphthalenyl)dimethylamine (11% of the moles of starting material, 0.011 mmol, 4.0 mg), cesium carbonate (1.5 equiv, 0.15 mmol, 48.9 mg) were dissolved in super dry tetrahydrofuran (1.0 mL) in a glove box. The mixture was stirred at 100 °C for 48 hours under an argon atmosphere. After the reaction was complete, the mixture was cooled to room temperature and the solvent was removed by rotary evaporation under reduced pressure. The product was isolated by chromatography on a 300-400 mesh silica gel column using petroleum ether: ethyl acetate = 100:1 as eluent. The product was dried under vacuum to give 28.0 mg, 51% yield, 99% enantiomeric excess. 1HNMR (500 MHz, CDC13) δ 8.04 (dd, J = 7.5, 4.5 Hz, 1H), 7.35 (t, J = 7.5 Hz, 1H), 7.29 (d, J = 4.0 Hz, 3H), 7.24 - 7.10 (m, 6H), 7.02 (t, J = 8.0 Hz, 1H), 6.94 (dd, J = 7.5, 3.5 Hz, 1H), 6.90 (t, J = 7.5 Hz, 2H), 6.84 (d, J = 7.5 Hz, 1H), 6.68 (s, 1H), 6.64 (d, J = 8.0 Hz, 1H), 4.62 (s, 1H), 4.28 (s, 1H), 4.21 (s, 1H), 4.17 (s, 5H), 3.54 (s, 3H). 13 C NMR (126 MHz, CDC13) δ 158.9, 143.3 (d, J = 29.1 Hz), 140.2 (d, J = 0.8 Hz), 138.7 (d, J = 14.1 Hz), 137.9 (dd, J = 17.4, 13.2 Hz), 134.0 (d, J = 0.9 Hz), 133.74, 133.70 (d, J = 19.8 Hz), 128.7, 128.36 (d, J = 5.4 Hz), 128.29 (dd, J = 22.9, 6.6 Hz), 128.2, 127.2, 121.6, 114.2, 112.0, 89.6 (d, J = 10.0 Hz), 87.7 (d, J = 2.2 Hz), 73.0 (d, J = 7.6 Hz), 70.7, 68.8, 66.8, 55.0. 31 P NMR (202 MHz, CDC13) δ -14.02.

[0066] Example 14

[0067] Synthesis of (1R)-1-[2-(diphenylphosphino)phenyl]-2-[3,5-dimethyl-4- methoxyphenyl]ferrocene:

[0068] A 25 mL Schlenk tube was oven dried at 630 °C for three times with a high temperature oven gun. After cooling, [2-(diphenylphosphino)phenyl]ferrocene (1.0 equiv, 0.10 mmol), 4-bromo-2,6-dimethylanisole (2.0 equiv, 0.2 mmol, 32 μί), 1,3-bis-(2,6-diisopropylphenyl)-imidazolyl-2-ylidene-(allyl) palladium chloride (5% of the raw material molar, 0.005 mmol, 2.9 mg), (R)-(3,5-dioxo-4-phospha-cycloheptyl[2,1-A,3,4-A']binaphthyl)dimethylamine (11% of the raw material molar, 0.011 mmol, 4.0 mg), cesium carbonate (1.5 equiv, 0.15 mmol, 48.9 mg) were dissolved in super dry tetrahydrofuran (1.0 mL) in a glove box. The mixture was stirred at 100 °C for 48 h under argon atmosphere. After the reaction was completed, the mixture was cooled to room temperature and the solvent was removed by rotary evaporation under reduced pressure. The product was isolated by column chromatography on 300-400 mesh silica gel using petroleum ether: ethyl acetate = 100: 1 as eluent. The product was dried under vacuum to give 29.7 mg in 51% yield with 92% enantiomeric excess. 1 HNMR (500 MHz, CDC13) δ 8.08-8.03 (m, 1H), 7.39-7.28 (m, 4H), 7.24-7.14 (m, 6H), 7.00-6.96 (m, 1H), 6.92 (d, J = 2.0 Hz, 2H), 6.80 (d, J = 3.0 Hz, 2H), 4.56 (s, 1H), 4.29 (dd, J = 5.5, 3.0 Hz, 2H), 4.20 (d, J = 4.0 Hz, 5H), 3.71 (d, J = 4.0 Hz, 3H), 2.13 (d, J = 3.5 Hz, 6H). 13 C NMR (126 MHz, CDC13) δ 155.2, 143.4 (d, J = 29.2 Hz), 138.6 (d, J = 13.8 Hz), 138.0 (dd, J = 43.8, 13.5 Hz), 134.0, 133.8 (d, J = 5.2 Hz), 133.6, 133.6 (dd, J = 19.8, 4.1 Hz), 129.6, 128.4 (d, J = 6.4 Hz), 128.3 (d, J = 3.2 Hz), 128.1 (d, J = 3.0 Hz), 128.0, 127.1, 89.5 (d, J = 10.2 Hz), 88.2 (d, J = 2.1 Hz), 72.7 (d, J = 8.0 Hz), 70.5, 68.6, 66.4, 59.7, 16.2. 31 PNMR (202 MHz, CDC13) δ -14.19.

[0069] Example 15

[0070] Synthesis of (1R)-1-[2-(diphenylphosphino)phenyl]-2-[4- phenoxyphenyl]ferrocene:

[0071] A 25 mL Schlenk tube was oven dried at 630 °C three times with a high temperature oven gun. After cooling, [2-(diphenylphosphino)phenyl]ferrocene (1.0 equiv, 0.10 mmol), 4-bromo diphenyl ether (2.0 equiv, 0.2 mmol, 35 μL), 1,3-bis-(2,6-diisopropylphenyl)-imidazolyl-2-ylidene-(allyl) palladium chloride (5% of the starting material, 0.005 mmol, 2.9 mg), (R)-(3,5-dioxo-4-phospha-cycloheptyl[2,1-A,3,4-A']dinaphthalenyl)dimethylamine (11% of the starting material, 0.011 mmol, 4.0 mg), cesium carbonate (1.5 equiv, 0.15 mmol, 48.9 mg) were dissolved in super dry tetrahydrofuran (1.0 mL) in a glove box. The mixture was stirred at 100 °C under argon atmosphere for 48 hours. After the reaction was completed, the mixture was cooled to room temperature and the solvent was removed by rotary evaporation under reduced pressure. The product was isolated by column chromatography on 300-400 mesh silica gel using petroleum ether: ethyl acetate = 100:1 as eluent. After drying under vacuum, 27.2 mg of product was obtained in 44% yield with 92% enantiomeric excess. 1 HNMR (400 MHz, CDC13) δ 8.04 (dd, J = 7.2, 4.4 Hz, 1H), 7.37-7.32 (m, 3H), 7.29-7.28 (m, 3H), 7.23-7.13 (m, 8H), 7.10 (t, J = 7.6 Hz, 1H), 7.02 (d, J = 7.6 Hz, 2H), 6.95-6.88 (m, 3H), 6.76 (d, J = 8.4 Hz, 2H), 4.59-4.56 (m, 1H), 4.27 (t, J = 2.4 Hz, 1H), 4.23-4.15 (m, 6H). 13C NMR (101 MHz, CDC13) δ 157.3, 155.4, 143.0 (d, J = 28.6 Hz), 138.7 (d, J = 14.2 Hz), 137.8 (dd, J = 13.3, 7.7 Hz), 133.88 (d, J = 1.4 Hz), 133.73 (dd, J = 20.8, 6.8 Hz), 133.7 (d, J = 1.5 Hz), 133.62, 130.0 (d, J = 40.4 Hz), 128.40, 128.38, 128.31 (d, J = 5.9 Hz), 128.2, 127.2, 123.2, 119.0, 118.1, 89.4 (d, J = 9.8 Hz), 87.6 (d, J = 2.4 Hz), 72.9 (d, J = 7.3 Hz), 70.6, 68.5, 66.7. 31 PNMR (162 MHz, CDC13) δ -13.60.

[0072] Example 16

[0073] Synthesis of (1R)-1-[2-(diphenylphosphino)phenyl]-2-[4- thioxomethylphenyl]ferrocene:

[0074] A 25 mL Schlenk tube was oven dried at 630 °C three times with a high temperature oven gun. After allowing to cool, [2-(diphenylphosphino)phenyl]ferrocene (1.0 equiv, 0.10 mmol), 4-bromo thioanisole (2.0 equiv, 0.2 mmol, 40.6 mg), 1,3-bis-(2,6-diisopropylphenyl)-imidazolyl-2-ylidene-(allyl) palladium chloride (5% of the moles of starting material, 0.005 mmol, 2.9 mg), (R)-(3,5-dioxo-4-phospha-cycloheptyl[2,1-A,3,4-A']dinaphthalenyl)dimethylamine (11% of the moles of starting material, 0.011 mmol, 4.0 mg), cesium carbonate (1.5 equiv, 0.15 mmol, 48.9 mg) were dissolved in super dry tetrahydrofuran (1.0 mL). The mixture was stirred at 100 °C under an argon atmosphere for 48 hours. After the reaction was complete, the mixture was cooled to room temperature and the solvent was removed by rotary evaporation under reduced pressure. The product was isolated by chromatography on a 300-400 mesh silica gel column using petroleum ether: ethyl acetate = 100:1 as eluent. The product was dried under vacuum to give 35.2 mg, 62% yield, with an enantiomeric excess of 96%. 1HNMR (500 MHz, CDC13) δ 8.04 (dd, J = 7.0, 4.5 Hz, 1H), 7.36 (t, J = 7.5 Hz, 1H), 7.28-7.27 (m, 3H), 7.23-7.17 (m, 2H), 7.16-7.11 (m, 4H), 7.10 (d, J = 8.0 Hz, 2H), 6.99 (d, J = 8.0 Hz, 2H), 6.94 (dd, J = 7.0, 3.5 Hz, 1H), 6.86 (t, J = 7.5 Hz, 2H), 4.58 (s, 1H), 4.29 (t, J = 2.5 Hz, 1H), 4.23 (s, 1H), 4.17 (s, 5H), 2.46 (s, 3H). 13 C NMR (126 MHz, CDC13) δ 143.1 (d, J = 28.9 Hz), 138.6 (d, J = 14.3 Hz), 137.8 (dd, J = 34.5, 13.1 Hz), 135.8 (d, J = 1.4 Hz), 135.4, 134.0 (d, J = 1.1 Hz), 133.7 (dd, J = 20.0, 2.6 Hz), 133.6 (d, J = 5.4 Hz), 129.4, 128.4 (dd, J = 11.5, 5.0 Hz), 128.22, 128.17, 127.2, 126.1, 89.6 (d, J = 9.9 Hz), 87.5 (d, J = 2.6 Hz), 73.0 (d, J = 7.3 Hz), 70.6, 63.4, 66.8, 16.0. 31 P NMR (202 MHz, CDC13) δ -13.91.

[0075] Example 17

[0076] Synthesis of (1R)-1-[2-(diphenylphosphino)phenyl]-2-[4- trimethylsilylphenyl]ferrocene:

[0077] A 25 mL Schlenk tube was oven dried at 630 °C three times with a high temperature oven gun, and after allowing to cool, [2-(diphenylphosphino)phenyl]ferrocene (1.0 equiv, 0.10 mmol), 1-bromo-4-trimethylsilphenyl (1.0 equiv, 0.1 mmol, 20 μί), 1,3-bis-(2,6-diisopropylphenyl)-imidazolyl-2-ylidene-(allyl)palladium (5% of the original moles, 0.005 mmol, 2.9 mg), (R)-(3,5-dioxo-4-phospha-cycloheptyl[2,1-A,3,4-A']binaphthyl)dimethylamine (11% of the original moles, 0.011 mmol, 4.0 mg), cesium carbonate (1.5 equiv, 0.15 mmol, 48.9 mg) were dissolved in super dry tetrahydrofuran (1.0 mL) in a glove box. The mixture was stirred at 100 °C for 48 hours under an argon atmosphere. After the reaction was complete, the mixture was cooled to room temperature and the solvent was removed by rotary evaporation under reduced pressure. The product was isolated by chromatography on a 300-400 mesh silica gel column using petroleum ether: ethyl acetate = 500: 1 as eluent. The product was dried under vacuum to give 53.5 mg, 90% yield, 97% enantiomeric excess. 1 HNMR (500 MHz, CDC13) δ 8.06 (dd, J = 7.5, 4.5 Hz, 1H), 7.36 (t, J = 7.5 Hz, 1H), 7.28-7.25 (m, 5H), 7.23-7.08 (m, 8H), 6.91 (dd, J = 7.5, 3.5 Hz, 1H), 6.80 (t, J = 7.5 Hz, 2H), 4.61 (s, 1H), 4.28 (t, J = 2.0 Hz, 1H), 4.22 (s, 1H), 4.18 (s, 5H), 0.26 (s, 9H). 13 C NMR (126 MHz, CDC13) δ 143.2 (d, J = 29.0 Hz), 139.4 (d, J = 1.5 Hz), 138.7 (d, J = 14.3 Hz), 137.9 (dd, J = 20.4, 15 Hz), 137.3, 134.0 (d, J = 1.3 Hz), 133.65, 133.64 (dd, J = 19.8, 13.4 Hz), 132.7, 128.4, 128.3 (dd, J = 10.0, 4.0 Hz), 128.2, 128.1 (d, J = 2.0 Hz), 127.2, 89.7 (d, J = 10.0 Hz), 87.9 (d, J = 2.8 Hz), 73.0 (d, J = 7.0 Hz), 70.7, 68.6, 66.8, -0.9. 31 P NMR (202 MHz, CDC13) δ -13.94.

[0078] Example 18

[0079] Synthesis of (1R)-1-[2-(diphenylphosphino)phenyl]-2-[4-fluorophenyl]ferrocene:

[0080] A 25 mL Schlenk tube was oven dried at 630 °C three times with a high temperature oven gun, after waiting to cool, [2-(diphenylphosphino)phenyl]ferrocene (1.0 equiv, 0.10 mmol), 4-bromo-fluorobenzene (2.0 equiv, 0.2 mmol, 22 μί), 1,3-bis-(2,6-diisopropylphenyl)-imidazolyl-2-ylidene-(allyl)palladium (5% of the moles of starting material, 0.005 mmol, 2.9 mg), (S)-(+)-(3,5-dioxa-4-phosphanorbornenyl-4-yl)-5H-dibenzo[B,F]azepine (11% of the moles of starting material, 0.011 mmol, 4.0 mg), cesium carbonate (1.5 equiv, 0.15 mmol, 48.9 mg) were dissolved in super-dry tetrahydrofuran (1.0 mL) in a glove box. The mixture was stirred at 100 °C for 48 h under an argon atmosphere. After the reaction was complete, the mixture was cooled to room temperature and the solvent was removed by rotary evaporation under reduced pressure. The product was isolated by column chromatography on 300-400 mesh silica gel using petroleum ether: ethyl acetate = 500: 1 as eluent. The product was dried under vacuum to give 25.8 mg, 48% yield, 96% enantiomeric excess. 1 H NMR (500 MHz, CDC13) δ 8.02 (dd, J = 7.0, 4.5 Hz, 1H), 7.38 - 7.27 (m, 4H), 7.23 - 7.10 (m, 8H), 6.93 (dd, J = 7.0, 3.5 Hz, 1H), 6.87 (t, J = 7.0 Hz, 2H), 6.77 (t, J = 9.0 Hz, 2H), 4.55 (s, 1H), 4.28 (t, J = 2.5 Hz, 1H), 4.22 (s, 1H), 4.17 (s, 5H). 13 C NMR (126 MHz, CDC13) δ 161.2 (d, J = 244.7 Hz), 142.7 (d, J = 28.9 Hz), 138.6 (d, J = 14.3 Hz), 137.6 (dd, J = 48.9, 13.0 Hz), 134.4 (dd, J = 3.0, 1.2 Hz), 133.9 (d, J = 1.0 Hz), 133.6 (dd, J = 19.9, 3.5 Hz), 133.5, 130.3 (d, J = 7.8 Hz), 128.3 (dd, J = 6.9, 1.6 Hz), 128.1, 128.1, 127.2, 114.4 (d, J = 21.3 Hz), 89.5 (d, J = 9.9 Hz), 87.2 (d, J = 2.4 Hz), 72.8 (d, J = 7.2 Hz), 70.5, 68.4, 66.6. 31PNMR (202 MHz, CDCI3) δ -13.76. 19 F NMR (471 MHz, CDCI3) δ -117.28.

[0081] Example 19

[0082] Synthesis of (1R)-1-[2-(diphenylphosphino)phenyl]-2-[4- trifluoromethylphenyl]ferrocene:

[0083] A 25 mL Schlenk tube was oven dried at 630 °C for three times with a high temperature oven gun. After cooling, [2-(diphenylphosphino)phenyl]ferrocene (1.0 eq, 0.10 mmol), 4-bromo-trifluorotoluene (2.0 eq, 0.2 mmol, 28 μL), tris(dibenzylideneacetone)dipalladium (5% of the raw material molar, 0.005 mmol, 2.9 mg), (R)-(3,5-dioxo-4-phospha-cycloheptyl[2,1-A,3,4-A']dinaphthalenyl)dimethylamine (11% of the raw material molar, 0.011 mmol, 4.0 mg), cesium carbonate (1.5 eq, 0.15 mmol, 48.9 mg) were dissolved in super dry tetrahydrofuran (1.0 mL) in a glove box. The mixture was stirred at 100 °C for 48 hours under argon atmosphere. After the reaction was completed, the mixture was cooled to room temperature, and the solvent was removed by rotary evaporation under reduced pressure. The product was isolated by column chromatography on 300-400 mesh silica gel using petroleum ether: ethyl acetate = 500: 1 as eluent. After drying under vacuum, 31.8 mg of product was obtained with a yield of 54% and an enantiomeric excess of 90%. 1 H NMR (500 MHz, CDCI3) δ 6.80 (dd, J = 7.9, 4.0 Hz, 1 H), 6.11 (d, J = 8.0 Hz, 1 H), 6.08 - 5.92 (m, 8H), 5.88 (d, J = 7.1 Hz, 1 H), 5.84 - 5.77 (m, 4H), 5.68 - 5.63 (m, 1 H), 5.50 (t, J = 7.6 Hz, 2H), 3.36 (s, 1 H), 3.08 (s, 1 H), 3.01 (s, 1 H), 2.91 (d, J = 2.9 Hz, 5H). 13C NMR (126 MHz, CDCI3) δ 143.5, 142.5 (d, J = 29.0 Hz), 138.9 (d, J = 14.5 Hz), 137.4 (dd, J = 74.0, 13.1 Hz), 134.1, 133.6 (d, J = 20.0 Hz), 133.4 (d, J = 5.0 Hz), 128.9, 128.6, 128.4 (d, J = 3.8 Hz), 128.2 (d, J = 6.6 Hz), 127.57 (q, J = 32.3 Hz), 127.5. 124.60 (q, J = 3.7 Hz), 124.59 (q, J = 274.7 Hz), 90.5 (d, J = 10.0 Hz), 85.9 (d, J = 3.3 Hz), 73.8 (d, J = 6.2 Hz), 70.8, 68.2, 67.4. 31 P NMR (202 MHz, CDCI3) δ -13.93. 19 F NMR (471 MHz, CDCI3) δ -62.26.

[0084] Example 20

[0085] Synthesis of (1R)-1-[2-(diphenylphosphino)phenyl]-2-[4- trifluoromethoxyphenyl]ferrocene:

[0086] A 25 mL Schlenk tube was oven dried at 630 °C three times with a high temperature oven gun, after waiting for cooling, [2-(diphenylphosphino)phenyl]ferrocene (1.0 eq, 0.10 mmol), 1-bromo-4-trifluoromethoxybenzene (2.0 eq, 0.2 mmol, 30 μί), 1,3-bis-(2,6-diisopropylphenyl)-imidazolyl-2-ylidene-(allyl) palladium chloride (5% of the raw material molar, 0.005 mmol, 2.9 mg), (R)-(3,5-dioxo-4-phospha-cycloheptyl[2,1-A,3,4-A']dinaphthalenyl)dimethylamine (11% of the raw material molar, 0.011 mmol, 4.0 mg), cesium carbonate (1.5 eq, 0.15 mmol, 48.9 mg) were dissolved in super dry tetrahydrofuran (1.0 mL). The mixture was stirred at 100 °C for 48 hours under argon atmosphere. After the reaction was completed, it was cooled to room temperature, and then the solvent was removed by rotary evaporation under reduced pressure. The product was obtained by silica gel column chromatography (300-400 mesh) using petroleum ether: ethyl acetate = 500: 1 as eluent, and dried under vacuum. The yield was 30.0 mg, 50% with an enantiomeric excess of 94%. 1HNMR (500 MHz, CDC13) δ 8.09-8.07 (m, 1H), 7.41 (t, J = 7.5 Hz, 1H), 7.29 (d, J = 4.9 Hz, 3H), 7.27-7.23 (m, 1H), 7.20 (d, J = 8.4 Hz, 3H), 7.17-7.09 (m, 4H), 6.95 (t, J = 7.3 Hz, 3H), 6.84 (t, J = 7.0 Hz, 2H), 4.61 (s, 1H), 4.33 (d, J = 2.2 Hz, 1H), 4.25 (s, 1H), 4.21 (s, 5H). 13 CNMR (126 MHz, CDC13) δ 147.3, 142.6 (d, J = 28.9 Hz), 139.0 (d, J = 14.4 Hz), 138.0, 137.5 (dd, J = 38.4, 13.1 Hz), 133.96, 133.69 (dd, J = 20.1, 4.7 Hz), 133.5 (d, J = 5.1 Hz), 130.0, 128.6, 128.4 (dd, J = 6.6, 2.1 Hz), 128.3 (d, J = 6.6 Hz), 127.5, 120.7 (q, J = 257.7 Hz), 120.2, 90.0 (d, J = 9.8 Hz), 86.5 (d, J = 2.9 Hz), 73.4 (d, J = 6.4 Hz), 70.7, 68.2, 67.1. 31 PNMR (202 MHz, CDC13) δ -13.73. 19 F NMR (471 MHz, CDC13) δ -57.72.

[0087] Example 21

[0088] Synthesis of (1R)-1-[2-(diphenylphosphino)phenyl]-2-[4- benzoate]ferrocene:

[0089] A 25 mL Schlenk tube was oven dried at 630 °C three times with a high temperature oven gun, and after allowing to cool, [2-(diphenylphosphino)phenyl]ferrocene (1.0 equiv, 0.10 mmol), methyl p-bromobenzoate (1.25 equiv, 0.125 mmol, 26.9 mg), 1,3-bis-(2,6-diisopropylphenyl)-imidazolyl-2-ylidene-(allyl)palladium (5% of the moles of starting material, 0.005 mmol, 2.9 mg), (R)-(3,5-dioxy-4-phospha-cycloheptyl[2,1-A,3,4-A']binaphthyl)dimethylamine (11% of the moles of starting material, 0.011 mmol, 4.0 mg), cesium carbonate (1.5 equiv, 0.15 mmol, 48.9 mg) were dissolved in super-dry tetrahydrofuran (1.0 mL) in a glove box. The mixture was stirred at 100 °C under an argon atmosphere for 48 hours. After the reaction was complete, the mixture was cooled to room temperature and the solvent was removed by rotary evaporation under reduced pressure. The product was isolated by chromatography on a 300-400 mesh silica gel column using petroleum ether: ethyl acetate = 30:1 as eluent. The product was dried under vacuum to give 40.6 mg, 70% yield, with an enantiomeric excess of 97%. 1 HNMR (500 MHz, CDC13) δ 8.03 (dd, J = 7.0, 4.5 Hz, 1H), 7.74 (d, J = 8.0 Hz, 2H), 7.37 (t, J = 7.5 Hz, 1H), 7.28-7.27 (m, 3H), 7.24-7.20 (m, 3H), 7.18-7.15 (m, 1H), 7.13-7.10 (m, 4H), 6.94 (dd, J = 7.5, 3.5 Hz, 1H), 6.86 (t, J = 7.0 Hz, 2H), 4.66 (s, 1H), 4.34 (t, J = 2.0 Hz, 1H), 4.27 (s, 1H), 4.17 (s, 5H), 3.90 (s, 3H). 13 C NMR (126 MHz, CDC13) δ 167.3, 144.8 (d, J = 1.1 Hz), 142.6 (d, J = 28.4 Hz), 138.8 (d, J = 14.3 Hz), 137.7 (d, J = 12.8 Hz), 137.1 (d, J = 12.8 Hz) 133.9, 133.7 (dd, J = 20.1, 4.9 Hz), 133.5 (d, J = 4.9 Hz), 129.0, 128.5, 128.4 (d, J = 20.3 Hz), 128.3 (dd, J = 10, 6.6 Hz), 127.4, 127.2, 90.1 (d, J = 9.9 Hz), 86.0 (d, J = 2.6 Hz), 73.8 (d, J = 6.8 Hz), 70.8, 68.6, 67.4, 52.0. 31 P NMR (202 MHz, CDC13) δ -13.70.

[0090] Example 22

[0091] Synthesis of (1R)-1-[2-(diphenylphosphino)phenyl]-2-[3-formylphenyl]ferrocene:

[0092] A 25 mL Schlenk tube was oven dried at 630 °C three times with a high temperature oven gun, and after waiting for it to cool, [2-(diphenylphosphino)phenyl]ferrocene (1.0 equiv, 0.10 mmol), 3'-bromoacetophenone (2.0 equiv, 0.2 mmol, 27 μL), 1,3-bis-(2,6-diisopropylphenyl)-imidazolyl-2-ylidene-(allyl)palladium (5% of the moles of starting material, 0.005 mmol, 2.9 mg), (R)-(3,5-dioxy-4-phospha-cycloheptyl[2,1-A,3,4-A']dinaphthalenyl)dimethylamine (11% of the moles of starting material, 0.011 mmol, 4.0 mg), cesium carbonate (1.5 equiv, 0.15 mmol, 48.9 mg) were dissolved in super-dry tetrahydrofuran (1.0 mL) in a glove box. The mixture was stirred at 100 °C under an argon atmosphere for 48 hours. After the reaction was complete, the mixture was cooled to room temperature and the solvent was removed by rotary evaporation under reduced pressure. The product was isolated by chromatography on a 300-400 mesh silica gel column using petroleum ether: ethyl acetate = 100:1 as eluent. The product was dried under vacuum to give 27.5 mg, 49% yield, with an enantiomeric excess of 98%. 1 HNMR (400 MHz, CDC13) δ 8.06 (ddd, J = 7.6, 4.4, 1.2 Hz, 1H), 7.69-7.65 (m, 2H), 7.42 (dt, J = 8.0, 1.2 Hz, 1H), 7.38 (td, J = 7.6, 1.2 Hz, 1H), 7.29-7.26 (m, 3H), 7.25-7.07 (m, 7H), 6.94 (ddd, J = 8.0, 3.6, 1.2 Hz, 1H), 6.89-6.82 (m, 2H), 4.67 (dd, J = 2.4, 1.6 Hz, 1H), 4.34 (t, J = 2.4 Hz, 1H), 4.26-4.24 (m, 1H), 4.18 (s, 5H), 2.30 (s, 3H). 13C NMR (101 MHz, CDC13) δ 198.3, 142.7 (d, J = 28.6 Hz), 139.5 (d, J = 1.3 Hz), 139.0 (d, J = 14.1 Hz), 137.5 (dd, J = 48.8, 12.6 Hz), 136.5, 134.0 (d, J = 1.0 Hz), 133.7 (d, J = 19.9 Hz), 133.6, 133.3, 129.0, 128.5, 128.36 (d, J = 9.3 Hz), 128.31 (dd, J = 15.6, 6.5 Hz), 128.1, 127.5, 125.4, 90.0 (d, J = 10 Hz), 86.5 (2.6 Hz), 73.4 (d, J = 6.8 Hz), 70.7, 68.4, 67.2, 26.6. 31 P NMR (162 MHz, CDC13) δ -13.82.

[0093] Example 23

[0094] Synthesis of (1R)-1-[2-(diphenylphosphino)phenyl]-2-[4-benzenesulfonyl]ferrocene:

[0095] A 25 mL Schlenk tube was oven dried at 630 °C three times with a high temperature oven gun. After allowing to cool, [2-(diphenylphosphino)phenyl]ferrocene (1.0 equiv, 0.10 mmol), 4-bromobenzenesulfonyl chloride (1.0 equiv, 0.1 mmol, 23.5 mg), 1,3-bis-(2,6-diisopropylphenyl)-imidazolyl-2-ylidene-(allyl) palladium chloride (5% of the moles of starting material, 0.005 mmol, 2.9 mg), (R)-(3,5-dioxo-4-phospha-cycloheptyl[2,1-A,3,4-A']dinaphthalenyl)dimethylamine (11% of the moles of starting material, 0.011 mmol, 4.0 mg), cesium carbonate (1.5 equiv, 0.15 mmol, 48.9 mg) were dissolved in super dry tetrahydrofuran (1.0 mL). The mixture was stirred at 100 °C under an argon atmosphere for 48 hours. After the reaction was complete, the mixture was cooled to room temperature and the solvent was removed by rotary evaporation under reduced pressure. The product was isolated by chromatography on a 300-400 mesh silica gel column eluted with petroleum ether: dichloromethane = 1:1. The product was dried under vacuum to give 35.4 mg, 59% yield, with an enantiomeric excess of 91%. 1HNMR (500 MHz, CDC13) δ 8.04 (dd, J = 7.5, 4.0 Hz, 1H), 7.60 (d, J = 7.5 Hz, 2H), 7.40 (t, J = 7.5 Hz, 1H), 7.30 (d, J = 7.5 Hz, 2H), 7.27-7.23 (m, 4H), 7.20-7.15 (m, 1H), 7.12, (d, J = 7.5 Hz, 2H), 7.07 (d, J = 7.5 Hz, 2H), 6.93 (dd, J = 7.5, 3.5 Hz, 1H), 6.82 (t, J = 7.5 Hz, 2H), 4.65 (s, 1H), 4.38 (s, 1H), 4.29 (s, 1H), 4.19 (s, 5H), 3.03 (s, 3H). 13 C NMR (126 MHz, CDC13) δ 146.4, 142.1 (d, J = 28.4 Hz), 139.0 (d, J = 14.4 Hz), 137.2 (dd, J = 48.6, 12.6 Hz), 137.1, 133.9, 133.7 (d, J = 19.9 Hz), 133.4 (d, J = 4.9 Hz), 129.1, 128.7, 128.5 (d, J = 4.5 Hz), 128.3 (dd, J = 8.8, 6.8 Hz), 127.7, 126.7, 90.6 (d, J = 9.9 Hz), 84.8 (d, J = 2.9 Hz), 74.3 (d, J = 6.0 Hz), 70.9, 68.4, 67.8, 44.6. 31 PNMR (202 MHz, CDC13) δ -13.67.

[0096] Example 24

[0097] Synthesis of (1R)-1-[2-(diphenylphosphino)phenyl]-2-[4-vinylphenyl]ferrocene:

[0098] A 25 mL Schlenk tube was oven dried at 630 °C for three times with a high temperature oven gun. After cooling, [2-(diphenylphosphino)phenyl]ferrocene (1.0 equiv, 0.10 mmol), 4- bromostyrene (2.0 equiv, 0.2 mmol, 26 μL), l,3-bis-(2,6-diisopropylphenyl)-imidazolyl-2- yl-(allyl)palladium chloride (5% of the raw material molar, 0.005 mmol, 2.9 mg), (R)- (3,5-dioxy-4-phospho-cycloheptyl[2,l-A',3,4-A']dinaphthalenyl)dimethylamine (11% of the raw material molar, 0.011 mmol, 4.0 mg), cesium pivalate (1.5 equiv, 0.15 mmol, 48.9 mg) were dissolved in super dry tetrahydrofuran (1.0 mL) in a glove box. The mixture was stirred at 100 °C for 72 hours under argon atmosphere. After the reaction was completed, the mixture was cooled to room temperature and the solvent was removed by rotary evaporation under reduced pressure. The product was isolated by column chromatography on 300-400 mesh silica gel using petroleum ether: ethyl acetate = 500: 1 as eluent. After drying in vacuum, 31.0 mg of product was obtained with a yield of 57% and an enantiomeric excess of 93%. 1 HNMR (500 MHz, CDC13) δ 8.05 (dd, J = 7.5, 4.5 Hz, 1H), 7.36 (t, J = 7.5 Hz, 1H), 7.29-7.28 (m, 3H), 7.21 (t, J = 7.5 Hz, 1H), 7.19-7.09 (m, 9H), 6.95 (dd, J = 7.5, 3.0 Hz, 1H), 6.86 (t, J = 7.0 Hz, 2H), 6.66 (dd, J = 17.5, 10.5 Hz, 1H), 5.70 (d, J = 17.5 Hz, 1H), 5.21 (d, J = 10.5 Hz, 1H), 4.62 (s, 1H), 4.30 (s, 1H), 4.25 (s, 1H), 4.18 (s, 5H). 13 C NMR (126 MHz, CDC13) δ 143.1 (d, J = 28.9 Hz), 138.6 (dd, J = 8.9, 7.6 Hz), 137.8 (dd, J = 29.3, 13.1 Hz), 136.9, 135.1, 134.0 (d, J = 1.0 Hz), 133.67 (dd, J = 20.0, 1.9 Hz), 133.64 (d, 5.1 Hz), 129.1, 128.4 (d, J = 2.3 Hz), 128.3 (d, J = 4.3 Hz), 128.2, 128.1 (d, J = 4.8 Hz), 127.2, 125.6, 112.9, 89.6 (d, J = 9.9 Hz), 87.5 (d, J = 2.5 Hz), 73.1 (d, J = 7.3 Hz), 70.7, 68.5, 66.9. 31PNMR (202 MHz, CDCI3) δ -13.91.

[0099] Example 25

[0100] Synthesis of (1R)-1-[2-(diphenylphosphino)phenyl]-2-[2-naphthyl]ferrocene:

[0101] A 25 mL Schlenk tube was oven dried at 630 °C three times with a high temperature oven gun, after waiting for cooling, in the glove box [2-(diphenylphosphino)phenyl]ferrocene (1.0 eq, 0.10 mmol), 2-bromonaphthalene (2.0 eq, 0.2 mmol, 41.4 mg), 1,3-bis-(2,6-diisopropylphenyl)-imidazolyl-2-ylidene-(allyl) palladium chloride (5% of the raw material molar, 0.005 mmol, 2.9 mg), N-dimethyl-[(R)-1,1'-spirobiindane-7,7'-diyl]phosphoramide (11% of the raw material molar, 0.011 mmol, 4.0 mg), cesium carbonate (1.5 eq, 0.15 mmol, 48.9 mg) were dissolved in super dry tetrahydrofuran (1.0 mL). The mixture was stirred at 100 °C for 48 hours under argon atmosphere. After the reaction was completed, it was cooled to room temperature, and then the solvent was removed by rotary evaporation under reduced pressure. The product was separated by 300-400 mesh silica gel column chromatography, eluted with petroleum ether: ethyl acetate = 500: 1, and dried under vacuum to obtain 34.9 mg of product, with a yield of 61%, and an enantiomeric excess value of 90%. 1 H NMR (500 MHz, CDCI3) δ 8.10 (dd, J = 7.8, 4.4 Hz, 1 H), 7.74 (d, 1 H), 7.60-7.52 (m, 3H), 7.45-7.34 (m, 4H), 7.31 (t, J = 3.3 Hz, 3H), 7.24 (td, J = 7.5, 1.3 Hz, 1 H), 7.19-7.14 (m, 2H), 7.05 (t, J = 7.3 Hz, 1 H), 6.98 (td, J = 7.2, 1.6 Hz, 3H), 6.82 (t, 2H), 4.75 (dd, J = 2.6, 1.4 Hz, 1 H), 4.39 (s, 1 H), 4.36-4.34 (m, 1 H), 4.23 (d, J = 1.1 Hz, 5H). 13C NMR (126 MHz, CDC13) δ 143.1 (d, J = 29.1 Hz), 138.7 (d, J = 14.2 Hz), 138.0 (d, J = 13.2 Hz), 137.2 (d, J = 13.1 Hz), 136.2, 133.9 (d, J = 0.9 Hz), 133.6, 133.5 (dd, J = 19.8, 1.4 Hz), 133.2, 131.9, 128.2 (d, J = 14.9 Hz), 128.1 (dd, J = 44.4, 14.2 Hz), 127.9, 127.7 (d, J = 1.9 Hz), 127.5, 127.1, 127.0, 126.8, 125.7, 125.1, 89.8 (d, J = 9.9 Hz), 87.6 (d, J = 2.5 Hz), 73.2 (d, J = 7.4 Hz), 70.6, 68.6, 66.9. 31 PNMR (202 MHz, CDC13) δ -14.01.

[0102] Example 26

[0103] Synthesis of (1R)-1-[2-(diphenylphosphino)phenyl]-2-[9-phenanthryl]ferrocene:

[0104] A 25 mL Schlenk tube was oven dried at 630 °C three times with a high temperature oven gun. After allowing to cool, [2-(diphenylphosphino)phenyl]ferrocene (1.0 eq, 0.10 mmol), 9-bromophenanthrene (2.0 eq, 0.2 mmol, 51.4 mg), palladium acetate (5% of the moles of starting material, 0.005 mmol, 2.9 mg), (R)-(3,5-dioxo-4-phospha-cycloheptyl[2,1-A,3,4-A']dinaphthalenyl)dimethylamine (11% of the moles of starting material, 0.011 mmol, 4.0 mg), cesium carbonate (1.5 eq, 0.15 mmol, 48.9 mg) were dissolved in super dry tetrahydrofuran (1.0 mL) in a glove box. The mixture was stirred at 100 °C under an argon atmosphere for 48 hours. After the reaction was complete, the mixture was cooled to room temperature and the solvent was removed by rotary evaporation under reduced pressure. The product was isolated by chromatography on a 300-400 mesh silica gel column using petroleum ether: ethyl acetate = 500:1 as eluent. The product was dried under vacuum to give 25.5 mg, 41% yield, 98% enantiomeric excess. 1H NMR (500 MHz, CDC13) δ 8.63 (d, J = 8.1 Hz, 1H), 8.58 (d, J = 8.3 Hz, 1H), 8.48 (s, 1H), 8.06 (d, J = 8.2 Hz, 1H), 7.97 (dd, J = 13.7, 8.2 Hz, 2H), 7.64 (p, J = 6.8 Hz, 2H), 7.50 (t, J = 7.5 Hz, 1H), 7.45 - 7.34 (m, 6H), 7.15 (t, J = 7.2 Hz, 1H), 7.07 (t, J = 7.8 Hz, 2H), 7.03 (d, J = 7.5 Hz, 1H), 6.96 (t, J = 7.4 Hz, 1H), 6.87 (t, J = 6.7 Hz, 3H), 4.62 (s, 1H), 4.47 (s, 2H), 4.34 (s, 5H). 13 C NMR (126 MHz, CDC13) δ 143.8 (d, J = 30.0 Hz), 138.7 (dd, J = 12.7, 9.9 Hz), 136.3 (d, J = 14.0 Hz), 134.8 (d, J = 1.8 Hz), 133.7 (d, J = 19.2 Hz), 133.5, 133.200 (d, J = 19.2 Hz), 133.197 (d, J = 5.8 Hz), 132.2, 131.7, 131.2, 130.0 (d, J = 21.0 Hz), 128.6 (d, J = 6.6 Hz), 128.5 (d, J = 2.4 Hz), 128.08, 128.07 (d, J = 5.9 Hz), 127.9, 127.8 (d, J = 6.3 Hz), 126.6 (d, J = 5.2 Hz), 126.4, 126.2, 126.0, 122.6, 122.4, 91.2, 90.7 (d, J = 9.6 Hz), 72.7, 71.4 (d, J = 11.8 Hz), 70.8, 66.4. 31 P NMR (202 MHz, CDC13) δ -14.67.

[0105] Example 27

[0106] Synthesis of (1R)-1-[2-(diphenylphosphino)phenyl]-2-[2-pyranyl]ferrocene:

[0107] A 25 mL Schlenk tube was oven dried at 630 °C three times with a high temperature oven gun, and after waiting to cool, [2-(diphenylphosphino)phenyl]ferrocene (1.0 equiv, 0.10 mmol), 2-bromopyrene (2.0 equiv, 0.2 mmol, 56.2 mg), l,3-bis-(2,6-diisopropylphenyl)-imidazolyl-2-ylidene-(allyl) palladium chloride (5% of the moles of starting material, 0.005 mmol, 2.9 mg), (R)-(3,5-dioxo-4-phospha-cycloheptyl[2,l-A',3,4-A']dinaphthalenyl)dimethylamine (11% of the moles of starting material, 0.011 mmol, 4.0 mg), cesium carbonate (1.5 equiv, 0.15 mmol, 48.9 mg) were dissolved in super dry tetrahydrofuran (1.0 mL) in a glove box. The mixture was stirred at 100 °C under an argon atmosphere for 48 hours. After the reaction was complete, the mixture was cooled to room temperature and the solvent was removed by rotary evaporation under reduced pressure. The product was isolated by chromatography on a 300-400 mesh silica gel column using petroleum ether: ethyl acetate = 500: 1 as eluent. The product was dried under vacuum to give 40.8 mg, 63% yield, with an enantiomeric excess of 97%. 1 H NMR (500 MHz, CDC13) δ 8.43 (d, J = 8.0 Hz, 1H), 8.34 (d, J = 9.5 Hz, 1H), 8.09 (d, J = 7.5 Hz, 1H), 8.06 - 7.89 (m, 6H), 7.78 (d, J = 9.5 Hz, 1H), 7.28 - 7.26 (m, 3H), 7.17 - 7.10 (m, 3H), 6.98 (td, J = 7.5, 1.5 Hz, 1H), 6.83 - 6.77 (m, 1H), 6.69 (t, J = 7.0 Hz, 1H), 6.63 (td, J = 7.5, 1.5 Hz, 2H), 6.52 (t, J = 7.0 Hz, 2H), 4.79 (d, J = 2.0 Hz, 1H), 4.50 (d, J = 2.5 Hz, 1H), 4.48 (d, J = 2.0 Hz, 1H), 4.29 (s, 5H). 13C NMR (126 MHz, CDC13) δ 143.8 (d, J = 30.7 Hz), 139.1 (d, J = 13.4 Hz), 137.1 (d, J = 2.8 Hz), 137.0 (d, J = 1.4 Hz), 135.0 (d, J = 2.0 Hz), 133.4, 133.3 (d, J = 19.3 Hz), 132.5 (d, J = 19.1 Hz), 131.4, 130.9, 130.8, 130.1, 130.0, 128.3 (d, J = 6.4 Hz), 128.1 (d, J = 9.5 Hz), 127.37 (d, J = 8.2 Hz), 127.35, 127.2, 126.9, 126.7, 126.6, 126.3 (d, J = 4.9 Hz), 125.6, 124.6 (d, J = 22.6 Hz), 124.5 (d, J = 5.0 Hz), 123.8, 91.9 (d, J = 9.7 Hz), 90.2 (d, J = 2.5 Hz), 72.1 (d, J = 8.1 Hz), 71.8, 70.9, 66.7. 31 P NMR (202 MHz, CDC13) δ -15.04.

[0108] Example 28

[0109] Synthesis of (1R)-1-[2-(diphenylphosphino)phenyl]-2-[6-quinolyl]ferrocene:

[0110] A 25 mL Schlenk tube was oven dried at 630 °C three times with a high temperature oven gun. After allowing to cool, [2-(diphenylphosphino)phenyl]ferrocene (1.0 equiv, 0.10 mmol), 6-bromoquinoline (1.25 equiv, 0.125 mmol, 26.0 mg), 1,3-bis-(2,6-diisopropylphenyl)-imidazolyl-2-ylidene-(allyl) palladium chloride (5% of the moles of starting material, 0.005 mmol, 2.9 mg), (R)-(3,5-dioxo-4-phospha-cycloheptyl[2,1-A,3,4-A']binaphthyl)dimethylamine (11% of the moles of starting material, 0.011 mmol, 4.0 mg), cesium carbonate (1.5 equiv, 0.15 mmol, 48.9 mg) were dissolved in super dry tetrahydrofuran (1.0 mL) in a glove box. The mixture was stirred at 100 °C for 48 hours under an argon atmosphere. After the reaction was complete, the mixture was cooled to room temperature and the solvent was removed by rotary evaporation under reduced pressure. The product was isolated by chromatography on a 300-400 mesh silica gel column using petroleum ether: ethyl acetate = 30:1 as eluent. The product was dried under vacuum to give 23.8 mg, 42% yield, 98% enantiomeric excess. 1HNMR (500 MHz, CDC13) δ 8.81 (d, J = 3.5 Hz, 1H), 8.10 (dd, J = 7.5, 4.5 Hz, 1H), 7.82 (d, J = 8.5 Hz, 1H), 7.78 (d, J = 8.5 Hz, 1H), 7.60 (d, J = 8.0 Hz, 1H), 7.40 (s, 1H), 7.37 (d, J = 7.5 Hz, 1H), 7.30 - 7.26 (m, 2H), 7.26 - 7.21 (m, 3H), 7.08 (td, J = 6.5, 1.5 Hz, 2H), 6.99 - 6.90 (m, 4H), 6.77 (t, J = 7.0 Hz, 2H), 4.73 - 4.71 (m, 1H), 4.40 - 4.38 (m, 1H), 4.34 - 4.33 (m, 1H), 4.21 (s, 5H). 13 C NMR (126 MHz, CDC13) δ 149.4, 146.8, 142.7 (d, J = 29.1 Hz), 138.8 (d, J = 14.2 Hz), 138.0 (d, J = 13.0 Hz), 137.5, 136.7 (d, J = 13.0 Hz), 135.7, 134.0, 133.4 (d, J = 19.9 Hz), 133.4 (d, J = 5.1 Hz), 131.3, 128.5, 128.20 (d, J = 9.8 Hz), 128.18, 127.94, 127.8 (d, J = 6.7 Hz), 127.3, 126.3, 90.2 (d, J = 9.9 Hz), 86.6 (d, J = 3.0 Hz), 73.6 (d, J = 6.4 Hz), 70.6, 68.3, 67.2. 31 P NMR (202 MHz, CDC13) δ -14.05.

[0111] Example 29

[0112] Synthesis of (1R)-1-[2-(diphenylphosphino)phenyl]-2-[3-bromo-6- trifluoromethylpyridyl]ferrocene:

[0113] A 25 mL Schlenk tube was oven dried at 630 °C three times with a high temperature oven gun, and after allowing to cool, [2-(diphenylphosphino)phenyl]ferrocene (1.0 equiv, 0.10 mmol), 5-bromo-2-trifluoromethylpyridine (1.25 equiv, 0.125 mmol, 28.2 mg), l,3-bis-(2,6-diisopropylphenyl)-imidazolyl-2-ylidene-(allyl) palladium chloride (5% of the moles of starting material, 0.005 mmol, 2.9 mg), (R)-(3,5-dioxo-4-phospha-cycloheptyl[2,l-A',3,4-A']dinaphthalenyl)dimethylamine (11% of the moles of starting material, 0.011 mmol, 4.0 mg), lithium tert-butoxide (1.5 equiv, 0.15 mmol, 48.9 mg) were dissolved in super-dry tetrahydrofuran (1.0 mL) in a glove box. The mixture was stirred at 100 °C under an argon atmosphere for 48 h. After the reaction was complete, the mixture was cooled to room temperature and the solvent was removed by rotary evaporation under reduced pressure. The product was isolated by chromatography on a 300-400 mesh silica gel column using petroleum ether: ethyl acetate = 100: 1 as eluent. After drying under vacuum, 27.9 mg of product was obtained in 47% yield with an enantiomeric excess of 94%. 1 H NMR (500 MHz, CDC13) δ 8.53 (d, J = 2.0 Hz, 1H), 8.08 (ddd, J = 7.5, 4.5, 1.0 Hz, 1H), 7.45-7.40 (m, 2H), 7.28 (d, J = 8.5 Hz, 2H), 7.26-7.22 (m, 3H), 7.16 (t, J = 7.0 Hz, 1H), 7.09 (td, J = 7.5, 1.5 Hz, 2H), 7.07-7.02 (m, 2H), 6.92 (ddd, J = 7.5, 3.5, 1.0 Hz, 1H), 6.83-6.78 (m, 2H), 4.65 (dd, J = 2.5, 1.5 Hz, 1H), 4.42 (t, J = 2.5 Hz, 1H), 4.34 (dt, J = 2.5, 1.0 Hz, 1H), 4.23-4.18 (m, 5H). 13C NMR (126MHz, CDCl3) δ149.6, 144.7 (q, J = 34.5Hz), 141.6 (d, J = 28.5Hz), 139.2, 139.0 (d, J = 14.3 Hz),136.9(dd,J=147.2,12.3Hz),135.9,134.1,133.7(dd,J=20.1,11.7Hz),133.3(d,J=4.9Hz ), 128.9, 128.44 (dd, J = 21.8, 15.2Hz), 128.35 (d, J = 1.8Hz), 127.9, 122.0 (q, J = 273.7Hz), 119. 5(dd,J=5.2,2.5Hz),91.0(d,J=9.9Hz),82.0(d,J=3.3Hz),74.5(d,J=5.6Hz),70.9,68.1,67.7. 31 PNMR (202MHz, CDCl3) δ -13.74. 19 F NMR (471MHz, CDCl3) δ -67.65.

[0114] Example 30

[0115] Synthesis of (1R)-1-[2-(diphenylphosphine)phenyl]-2-[5-(1-methyl-1H-indazole)]ferrocene:

[0116] The 25 mL Schlenk tubes were dried three times at 630 °C using a high-temperature drying gun. After cooling, [2-(diphenylphosphine)phenyl]ferrocene (1.0 equivalent, 0.10 mmol), 5-bromo-1-methyl-1H-indazole (2.0 equivalent, 0.2 mmol, 42.6 mg), and 1,3-bis-(2,6-diisopropylphenyl)-imidazolyl-2-ylidene-(allyl)palladium chloride (5% of the molar amount of the starting materials, 0.0 mg) were added in a glove box. The reaction mixture of (0.011 mmol, 4.0 mg) of dimethylamine (11% of the starting material), cesium carbonate (1.5 equivalent, 0.15 mmol, 48.9 mg), and ultra-dry tetrahydrofuran (1.0 mL) was dissolved in 1.0 mL of ultra-dry tetrahydrofuran. The mixture was stirred at 100 °C under an argon atmosphere for 48 hours. After the reaction was complete, the mixture was cooled to room temperature, and the solvent was removed by rotary evaporation under reduced pressure. The product was separated by a 300-400 mesh silica gel column, eluted with petroleum ether:ethyl acetate = 30:1, and dried under vacuum to give 36.3 mg of product, yield 63%, with an enantiomeric excess of 90%. 11H NMR (500 MHz, CDCl3) δ 8.10 (ddd, J = 7.5, 4.5, 1.0 Hz, 1H), 7.83 (d, J = 1.0 Hz, 1H), 7.41 (dd, J = 8.5, 0.5 Hz, 1H), 7.37 (td, J = 7.5, 1.0 Hz, 1H), 7.29 - 7.26 (m, 3H), 7.23 (dd, J = 7.5, 1.0 Hz, 1H), 7.14 (dd, J = 8.5, 1.5 Hz, 1H), 7.13 - 7.09 (m, 2H), 7.04 (t, J = 7.5 Hz, 1H), 6.99 - 6.94 (m, 3H), 6.88 (d, J = 1.0 Hz, 1H), 6.81 - 6.76 (m, 2H), 4.71 (dd, J = 2.5, 1.5 Hz, 1H), 4.38 (t, J = 2.5 Hz, 1H), 4.31 (dt, J = 2.5, 1.5 Hz, 1H), 4.21 (s, 5H), 3.76 (s, 3H). 13 13C NMR (126 MHz, CDCl3) δ 143.3 (d, J = 29.6 Hz), 134.0, 138.6 (dd, J = 91.0, 13.4 Hz), 137.2 (d, J = 13.0 Hz), 137.1 (d, J = 0.9 Hz), 134.2 (d, J = 1.5 Hz), 133.7 (d, J = 5.2 Hz), 133.5 (dd, J = 19.8, 14.7 Hz), 132.5, 128.5 (d, J = 21.6 Hz), 128.1 (dd, J = 40.1, 6.9 Hz), 128.0 (s), 127.4, 122.9, 122.3, 119.8, 108.4, 90.4 (d, J = 10.2 Hz), 88.1 (d, J = 2.6 Hz), 73.4 (d, J = 6.6 Hz), 70.7 (s), 68.5, 67.0. 31 31P NMR (202 MHz, CDCl3) δ -14.43.

[0117] Example 31

[0118] A 25 mL Schlenk tube was oven dried at 630 °C three times with a hot gun, and after waiting to cool, 1 '-phenyl-1 -[2-(diphenylphosphino)phenyl]ferrocene (1.0 equiv, 0.10 mmol, 52.2 mg), 4-bromoanisole (2.0 equiv, 0.2 mmol, 26 μί), 1,3-bis-(2,6-diisopropylphenyl)-imidazolyl-2-ylidene-(allyl) palladium chloride (5% of the moles of starting material, 0.005 mmol, 2.9 mg), (R)-(3,5-dioxo-4-phospha-cycloheptyl[2,1-A,3,4-A']binaphthyl)dimethylamine (11% of the moles of starting material, 0.011 mmol, 4.0 mg), cesium carbonate (1.5 equiv, 0.15 mmol, 48.9 mg) were dissolved in ultradry toluene (1.0 mL) in a glove box. The mixture was stirred at 100 °C for 48 h under an argon atmosphere. After the reaction was complete, the mixture was cooled to room temperature, and the solvent was removed by rotary evaporation under reduced pressure. The product was isolated by chromatography on a 300-400 mesh silica gel column using petroleum ether: ethyl acetate = 500: 1 as eluent. The product was dried under vacuum to give 18.8 mg, 30% yield, 97% enantiomeric excess. 1 H NMR (500 MHz, CDC13) δ 8.01 (dd, J = 6.5, 4.5 Hz, 1H), 7.39 - 7.35 (m, 2H), 7.31 (td, J = 7.5, 1.0 Hz, 1H), 7.27 (dd, J = 7.0, 3.5 Hz, 3H), 7.22 (t, J = 7.5 Hz, 2H), 7.19 - 7.14 (m, 3H), 7.14 - 7.09 (m, 4H), 6.99 (d, J = 8.5 Hz, 2H), 6.92 (dd, J = 7.0, 3.0 Hz, 1H), 6.86 (dd, J = 11.5, 4.0 Hz, 2H), 6.59 (d, J = 8.5 Hz, 2H), 4.69 - 4.64 (m, 1H), 4.62 - 4.57 (m, 1H), 4.37 - 4.33 (m, 1H), 4.31 (d, J = 1.0 Hz, 1H), 4.29 (d, J = 1.0 Hz, 1H), 4.07 - 4.05 (m, 2H), 3.76 (s, 3H). 13C NMR (126 MHz, CDC13) δ 157.9, 143.0 (d, J = 29.0 Hz), 138.5 (d, J = 14.2 Hz), 138.2, 137.9 (dd, J = 17.4, 13.3 Hz), 134.1 (d, J = 0.9 Hz), 133.7 (d, J = 4.5 Hz), 133.6 (dd, J = 19.8, 6.5 Hz), 130.1 (d, J = 1.1 Hz), 130.0, 128.4 (d, J = 11.6 Hz), 128.3 (d, J = 11.8 Hz), 128.2, 128.1, 127.1, 126.4, 126.1, 113.2, 89.5 (d, J = 9.9 Hz), 88.5 (d, J = 2.5 Hz), 86.3, 74.4 (d, J = 7.5 Hz), 72.6 (d, J = 48.6 Hz), 70.7, 69.2, 68.4 (d, J = 72.3 Hz), 55.3. 31 PNMR (202 MHz, CDC13) δ -13.89.

[0119] Example 32

[0120] A 25 mL Schlenk tube was oven dried at 630 °C three times with a high temperature oven gun. After cooling, 1 '-p-methoxyphenyl-1-[2-(diphenylphosphino)phenyl]ferrocene (1.0 eq, 0.10 mmol, 55.2 mg), 4-bromoanisole (2.0 eq, 0.2 mmol, 26 μL), 1,3-bis-(2,6-diisopropylphenyl)-imidazolyl-2-ylidene-(allyl) palladium chloride (5% of the moles of starting material, 0.005 mmol, 2.9 mg), (R)-(3,5-dioxo-4-phospha-cycloheptyl[2,1-A,3,4-A']dinaphthalenyl)dimethylamine (11% of the moles of starting material, 0.011 mmol, 4.0 mg), cesium carbonate (1.5 eq, 0.15 mmol, 48.9 mg) were dissolved in super dry tetrahydrofuran (1.0 mL). The mixture was stirred at 100 °C under argon atmosphere for 48 hours. After the reaction was completed, the mixture was cooled to room temperature and the solvent was removed by rotary evaporation under reduced pressure. The product was isolated by column chromatography on 300-400 mesh silica gel using petroleum ether: ethyl acetate = 500:1 as eluent. After drying under vacuum, 19.5 mg of product was obtained in 30% yield with an enantiomeric excess of 93%. 1H NMR (500 MHz, CDC13) δ 8.00 (ddd, J = 7.5, 4.5, 1.0 Hz, 1H), 7.33 - 7.26 (m, 4H), 7.25 (d, J = 3.0 Hz, 2H), 7.19 - 7.14 (m, 2H), 7.11 (ddd, J = 15.0, 7.5, 1.5 Hz, 4H), 7.00 - 6.95 (m, 2H), 6.91 (ddd, J = 7.5, 3.5, 1.0 Hz, 1H), 6.88 - 6.82 (m, 2H), 6.77 - 6.73 (m, 2H), 6.61 - 6.53 (m, 2H), 4.57 (dt, J = 2.5, 1.5 Hz, 1H), 4.51 (dt, J = 2.5, 1.5 Hz, 1H), 4.34 (dd, J = 2.5, 1.5 Hz, 1H), 4.30 - 4.23 (m, 2H), 4.08 - 4.02 (m, 2H), 3.81 (s, 3H), 3.76 (s, 3H). 13 C NMR (126 MHz, CDC13) δ 158.2, 157.8, 143.2 (d, J = 29.2 Hz), 138.5 (d, J = 14.1 Hz), 138.0 (dd, J = 18.3, 13.3 Hz), 134.1 (d, J = 1.2 Hz), 133.7 (d, J = 5.3 Hz), 133.6 (d, J = 4.9 Hz), 130.1 (dd, J = 8.3, 7.1 Hz), 130.0, 128.4, 128.3 (d, J = 7.0 Hz), 128.1 (d, J = 7.9 Hz), 128.1, 127.4, 127.1, 113.9, 113.2, 89.4 (d, J = 10.0 Hz), 88.5 (d, J = 2.6 Hz), 86.8, 74.3 (d, J = 7.5 Hz), 72.2, 71.8, 70.5, 69.0, 68.3, 67.6 (d, J = 17.9 Hz), 55.4, 55.3. 31 P NMR (202 MHz, CDC13) δ -13.93.

[0121] Example 33

[0122] Synthesis of (1R)-1-[2-(dicyclohexylphosphino)phenyl]-2-[4- methoxyphenyl]ferrocene:

[0123] A 25 mL Schlenk tube was oven dried at 630 °C for three times with a high temperature oven gun. After cooling down, [2-(dicyclohexylphosphino)phenyl]ferrocene (1.0 equiv, 0.10 mmol, 45.7 mg), 4-bromoanisole (2.0 equiv, 0.2 mmol, 26 μί), 1,3-bis-(2,6-diisopropylphenyl)-imidazolyl-2-ylidene-(allyl) palladium chloride (5% of the raw material molar, 0.005 mmol, 2.9 mg), (R)-(3,5-dioxo-4-phospha-cycloheptyl[2,1-A,3,4-A']binaphthyl)dimethylamine (11% of the raw material molar, 0.011 mmol, 4.0 mg), cesium carbonate (1.5 equiv, 0.15 mmol, 48.9 mg) were dissolved in super dry 1,4-dioxane (1.0 mL) in a glove box. The mixture was stirred at 100 °C for 72 h under argon atmosphere. After the reaction was completed, the mixture was cooled to room temperature, and the solvent was removed by rotary evaporation under reduced pressure. The product was isolated by column chromatography on 300-400 mesh silica gel using petroleum ether: ethyl acetate = 500: 1 as eluent. After drying under vacuum, 22.8 mg of product was obtained with a yield of 39% and an enantiomeric excess of 96%. 1 H NMR (500 MHz, CDC13) δ 8.18 (d, J = 3.5 Hz, 1H), 7.41 - 7.32 (m, 2H), 7.29 (d, J = 7.0 Hz, 1H), 7.13 (d, J = 8.5 Hz, 2H), 6.65 (d, J = 8.5 Hz, 2H), 4.62 (s, 1H), 4.34 (s, 2H), 4.17 (s, 5H), 3.73 (s, 3H), 1.71 - 1.42 (m, 11H), 1.34 (d, J = 7.5 Hz, 1H), 1.20 - 1.01 (m, 4H), 0.98 - 0.81 (m, 6H). 13 C NMR (126 MHz, CDC13) δ 157.9, 144.8 (d, J = 28.0 Hz), 137.2 (d, J = 21.6 Hz), 133.8 (d, J = 5.2 Hz), 132.5 (d, J = 2.8 Hz), 131.3, 130.2, 127.8, 126.2, 113.2, 91.2 (d, J = 9.3 Hz), 88.1 (d, J = 3.5 Hz), 73.7 (d, J = 5.4 Hz), 70.5, 67.2, 66.1, 55.3, 35.8 (d, J = 15.7 Hz), 33.3 (d, J = 13.8 Hz), 30.9 (d, J = 16.0 Hz), 30.0 (d, J = 18.3 Hz), 28.8 (dd, J = 13.1, 9.7 Hz), 27.5 (dd, J = 15.9, 9.1 Hz), 27.2 (dd, J = 10.3, 6.1 Hz), 26.5 (d, J = 14.2 Hz).31 PNMR (202 MHz, CDC13) δ -11.23.

[0124] Example 34

[0125] Synthesis of (1R)-1-[2-(diisopropylphosphino)phenyl]-2-[4- methoxyphenyl]ferrocene:

[0126] A 25 mL Schlenk tube was oven dried at 630 °C for three times with a high temperature oven gun. After cooling, [2-(diisopropylphosphino)phenyl]ferrocene (1.0 eq, 0.10 mmol, 37.7 mg), 4-bromoanisole (2.0 eq, 0.2 mmol, 26 μL), 1,3-bis-(2,6-diisopropylphenyl)-imidazolyl-2-ylidene-(allyl) palladium chloride (10% of the raw material molar, 0.010 mmol, 5.8 mg), (R)-(3,5-dioxo-4-phospha-cycloheptyl[2,1-A,3,4-A']dinaphthalenyl)dimethylamine (22% of the raw material molar, 0.022 mmol, 8.0 mg), potassium phosphate (1.5 eq, 0.15 mmol, 48.9 mg) were dissolved in super dry tetrahydrofuran (1.0 mL) in a glove box. The mixture was stirred at 150 °C for 48 hours under argon atmosphere. After the reaction was completed, the mixture was cooled to room temperature, and the solvent was removed by rotary evaporation under reduced pressure. The product was isolated by 300-400 mesh silica gel column chromatography using petroleum ether: ethyl acetate = 500: 1 as eluent. After drying under vacuum, 15.2 mg of product was obtained with a yield of 32% and an enantiomeric excess of 97%. 1 HNMR (500 MHz, CDC13) δ 8.17 (s, 1H), 7.38 (t, J = 7.0 Hz, 1H), 7.34 (d, J = 6.5 Hz, 1H), 7.29 (d, J = 7.0 Hz, 1H), 7.12 (d, J = 8.5 Hz, 2H), 6.64 (d, J = 8.5 Hz, 2H), 4.62 (s, 1H), 4.36 (s, 2H), 4.16 (s, 5H), 3.73 (s, 3H), 1.88-1.75 (m, 2H), 0.89-0.79 (m, 9H), 0.26 (dd, J = 13.0, 7.0 Hz, 3H). 13C NMR (126 MHz, CDCI3) δ 157.9, 144.6 (d, J = 27.3 Hz), 137.4 (d, J = 21.8 Hz), 133.8 (d, J = 4.8 Hz), 132.2 (d, J = 2.2 Hz), 131.4, 130.1, 128.0, 126.2, 113.2, 90.9 (d, J = 8.4 Hz), 88.0 (d, J = 3.4 Hz), 73.8 (d, J = 5.5 Hz), 70.5, 67.4, 66.1, 55.4, 25.6 (d, J = 15.2 Hz), 23.3 (d, J = 13.0 Hz), 20.7 (d, J = 17.2 Hz), 19.8 (d, J = 20.8 Hz), 19.2 (d, J = 14.5 Hz), 18.9 (d, J = 6.9 Hz). 31 PNMR (202 MHz, CDCI3) δ -3.77.

[0127] Example 35

[0128] Use of planar chiral aryl substituted ferrocenyl monophosphine ligands:

[0129] The ligands obtained according to the present application are used in the following reactions:

[0130]

[0131] wherein L* is the ligand prepared in example 1, 16, 18, 19, 24, 25.

[0132] The reaction method is as follows:

[0133] A 25 ml Schlenk tube was oven dried at 630 °C for three times with a high temperature oven gun. After cooling, (E)-methyl 2-((4-bromobenzylidene)amino)acetate (1.0 eq, 0.20 mmol, 51.0 mg), 1-phenyl-1 H-pyrrole-2,5-dione (2.0 eq, 0.4 mmol, 69.2 mg), silver acetate (1 % of the raw material molar amount, 0.002 mmol, 0.4 mg), planar chiral aryl substituted ferrocenyl monophosphine ligand (2.4% of the raw material molar amount, 0.0024 mmol), triethylamine (20% of the raw material molar amount, 0.04 mmol, 5.6 μl) were dissolved in ultra-dry dichloromethane (0.0 ml) in a glove box. The mixture was stirred at room temperature for 48 hours under argon atmosphere. After the reaction was completed, the solvent was removed by rotary evaporation under reduced pressure, and the product (1 S, 3R, 3aS, 6aR)-methyl 3-(4-oxophenyl)-4,6-dioxo-5-phenylacetylpyrrolo[3,4-c]pyrrole-1 -carboxylate was obtained by silica gel column chromatography (300-400 mesh) using petroleum ether: ethyl acetate = 5:1 as eluent and vacuum drying.

[0134] When the ligand prepared in Example 1 was used, the product was obtained in a yield of 86% with an enantiomeric excess of 96%, when the ligand prepared in Example 16 was used, the product was obtained in a yield of 79% with an enantiomeric excess of 95%, when the ligand prepared in Example 18 was used, the product was obtained in a yield of 83% with an enantiomeric excess of 96%, when the ligand prepared in Example 19 was used, the product was obtained in a yield of 93% with an enantiomeric excess of 99%, when the ligand prepared in Example 24 was used, the product was obtained in a yield of 79% with an enantiomeric excess of 98%, when the ligand prepared in Example 25 was used, the product was obtained in a yield of 89% with an enantiomeric excess of 95%.

Claims

1. A method for preparing a planar chiral aryl-substituted ferrocene monophosphine ligand, characterized in that, Includes the following steps: Using the compound of Formula 1 as a raw material and divalent palladium as a catalyst, under the protection of an inert gas, in an organic solution, with the participation of a base and a chiral ligand, the reaction temperature is controlled at 100~150℃. The raw material and the aromatic halide are reacted with the catalyst to prepare aryl-substituted ferrocene monophosphine ligands through a hydrocarbon activation reaction. The structural formula of the aryl-substituted ferrocene monophosphine ligand is shown in Formula 2. ， ； Among them, R 1 Independently selected from phenyl, cyclohexyl, or isopropyl; R 2 Selected from hydrogen atom, phenyl or p-methoxyphenyl; It can be polysubstituted, monosubstituted, or unsubstituted benzene, biphenyl, naphthalene, phenanthrene, pyrene, pyridine, indazole, or quinoline; The substituents are independently selected from alkyl, alkoxy, phenoxy, alkylthio, alkoxy, halogen, haloalkyl, haloalkoxy, ester, acyl, sulfone or unsaturated hydrocarbon groups.

2. The preparation method according to claim 1, characterized in that, The aromatic halogenated product is .

3. The preparation method according to claim 1, characterized in that, The catalyst is one of palladium acetate, tris(dibenzylidene indacetone) dipalladium, allyl palladium chloride dimer, or 1,3-bis-(2,6-diisopropylphenyl)-imidazolyl-2-ylidene-(allyl)palladium chloride.

4. The preparation method according to claim 1, characterized in that, The chiral ligands are selected from R-(+)-1,1'-binaphthyl-2,2'-bis(diphenylphosphine), (S)-1-(diphenylphosphine)-2-[(S)-4-tert-butyloxazoline-2-yl]ferrocene, (S)-(+)-(3,5-dioxa-4-phosphacyclohepten[2,1-A; One of the following: [3,4-A']dinaphth-4-yl)-5H-dibenzo[B,F]azapyrrolidone, (R)-(-)-(3,5-dioxo-4-phospho-cycloheptyl[2,1-A,3,4-A']dinaphthyl)dimethylamine, N-dimethyl-[(R)-1,1'-spirodihydroindene-7,7'-diyl]phosphite, or (3AR,8AR)-(-)-(2,2-dimethyl-4,4,8,8-tetraphenyl-tetrahydro-[1,3]dioxo[4,5-E][1,3,2]dioxophospho-6-YL)dimethylamine.

5. The preparation method according to claim 1, characterized in that, The molar ratio of the catalyst, chiral ligand, raw material and aromatic halogenated compound is 5~10%:11~22%:1:1~2.

6. The preparation method according to claim 1, characterized in that, The solvent of the organic solution is one or a mixture of toluene, tetrahydrofuran, or 1,4-dioxane.

7. The preparation method according to claim 1, characterized in that, The alkali is one of potassium phosphate, cesium carbonate, lithium tert-butoxide, or cesium neopentanoate.

8. The preparation method according to claim 1, characterized in that, The molar ratio of the alkali to the raw material is 1~2:

1.

9. The preparation method according to claim 8, characterized in that, The molar ratio of the alkali to the raw material is 1.5:

1.

10. The aryl-substituted ferrocene monophosphine ligands with planar chirality prepared by any of the preparation methods described in claims 1-9.

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