Preparation method of lipid chain substituted biphenyl type or phenylpyrrole type chiral monophosphine ligand

Abstract

The present invention discloses a method for preparing a lipid-chain-substituted biphenyl-type or phenylpyrrole-type chiral monophosphine ligand. The method comprises: using the biphenyl-type or phenylpyrrole-type monophosphine ligand as a raw material, controlling the reaction temperature at 70-150°C in an organic solution under the protection of an inert gas, and subjecting the raw material to an asymmetric carbon-hydrogen activation reaction with an aliphatic olefin, aliphatic alkyne, or a derivative thereof, catalyzed by a monovalent iridium catalyst and in the presence of the chiral ligand. This synthetic route has not been reported in the literature, and the raw materials are inexpensive and readily available. The unit operations are simple, the equipment requirements are low, and it is suitable for rapidly constructing a new chiral monophosphine ligand library.

Description

Technical Field

[0001] The invention belongs to the field of organic synthesis, and particularly relates to a method for preparing a lipid chain-substituted biphenyl-type or phenylpyrrole-type chiral monophosphine ligand. Background Art

[0002] Asymmetric transition metal-catalyzed reactions are closely linked to the development of chiral ligands. Chiral phosphine ligands, as the most widely used ligands in the increasingly popular field of cross-coupling, are increasingly attracting attention from synthetic chemists. Among them, MOP-type ligands, such as biaryl or binaphthyl ligands with axial chirality, have been extensively studied for their application in asymmetric transition metal-catalyzed reactions, such as asymmetric addition reactions of olefins and ketones to carbonyl groups, achieving excellent results. However, the lengthy synthesis steps for these chiral phosphine ligands (the first step involves synthesis of biphenylboronic acid, the second involves Suzuki reaction, the third step involves cross-coupling reaction to prepare the phosphine ligand, and the fourth step involves chiral resolution), limited substituent groups, a single structure, and low overall yields. These issues significantly hinder the development and application of these ligands. Summary of the Invention

[0003] To address the above problems, the present invention provides a new method for preparing a lipid chain-substituted biphenyl-type or phenylpyrrole-type chiral monophosphine ligand. The method has simple steps and can construct a lipid chain-substituted chiral monophosphine ligand in just one step. The method has good yield, high chemical selectivity and stereoselectivity, and is suitable for the rapid preparation of this type of chiral monophosphine ligand.

[0004] The technical solution adopted by the present invention to solve the technical problem is:

[0005] A method for preparing a lipid chain-substituted biphenyl-type or phenylpyrrole-type chiral monophosphine ligand comprises the following steps:

[0006] Using a biphenyl or phenylpyrrole monophosphine ligand as a raw material, under the protection of an inert gas, in an organic solution, the reaction temperature is controlled at 70-150° C., and the raw material and a fatty chain compound undergo an asymmetric carbon-hydrogen activation reaction with the participation of a chiral ligand to obtain the fatty chain-substituted biphenyl or phenylpyrrole chiral monophosphine ligand;

[0007] The catalyst is monovalent iridium;

[0008] The fatty chain compound is a fatty olefin, a fatty alkyne or a derivative thereof;

[0009] The structural formula of fatty olefins or their derivatives is ;

[0010] The structural formula of aliphatic alkyne or its derivatives is ;

[0011] R 4are independently selected from ester, alkyl or aryl groups.

[0012] Preferably, R 4 Selected from an ester group, a C1~C5 alkyl group or an unsubstituted aryl group.

[0013] Preferably, the monovalent iridium comes from one or more of (1,5-cyclooctadiene)iridium chloride (I) dimer, bicyclooctene iridium chloride (I) dimer, bis(1,5-cyclooctadiene)-iridium trifluoromethanesulfonate, bis(1,5-cyclooctadiene)iridium tetrafluoroborate (I) or di(ethylene)iridium chloride dimer; preferably, the monovalent iridium comes from (1,5-cyclooctadiene)iridium chloride (I) dimer.

[0014] Preferably, the molar ratio of the catalyst, chiral ligand, raw material and fatty chain compound is 5%:11%:1:5~10.

[0015] Preferably, the organic solvent is a mixture of one or more of toluene, trifluorotoluene, p-xylene, m-xylene, o-xylene, tetrahydrofuran or 1,4-dioxane; the preferred organic solvent is toluene.

[0016] Preferably, the chiral ligand is selected from (R)-(-)-(3,5-dioxo-4-phospho-cycloheptyl[2,1-A,3,4-A']dinaphthyl)dimethylamine, N-dimethyl-[(R)-1,1'-spirodihydroindane-7,7'-diyl]phosphoramidite, (3aR,8aR)-(2,2-dimethyl-4,4,8,8-tetraphenyl-tetrahydro-[1,3]dioxazolo[4,5- e][1,3,2]dioxaphosphinoheptan-6-yl)dimethylamine or (R)-(+)-(3,5-dioxa-4-phosphinoheptan-6-yl)-5-hydrogen-dibenzo[b,f]azepine; the preferred chiral ligand is (R)-(-)-(3,5-dioxa-4-phosphinoheptan-6-yl)dimethylamine.

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

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

[0019] Preferably, the raw material is selected from the compound of formula 1 or the compound of formula 11:

[0020] , ,

[0021] Among them, R 1 are independently selected from substituted or unsubstituted aromatic groups; R 2 、R 3independently selected from hydrogen, methyl, methoxy, aryl, halogen or trifluoromethyl; is a substituted or unsubstituted benzene ring, naphthalene ring, phenanthrene ring, pyrene ring, quinoline, acenaphthene, dibenzofuran ring or piperonyl ring.

[0022] Preferably, R 1 is selected from halogen-substituted aromatic groups or unsubstituted aromatic groups. More preferably, R 1 is selected from halophenyl, phenyl or thienyl.

[0023] The structures of the product of the reaction of the compound of formula 1 with a fatty olefin or a derivative thereof, and the product of the reaction of the compound of formula 1 with a fatty alkyne or a derivative thereof are shown in formulas 3 and 7, respectively: , .

[0024] When the compound of formula 1 is a binaphthyl monophosphine ligand, it may be a 1,1'-binaphthyl monophosphine ligand or a 1,2-binaphthyl monophosphine ligand.

[0025] The structure of the product of the reaction of the compound of formula 11 with a fatty alkyne or a derivative thereof is shown in formula 12:

[0026] .

[0027] Some chemical reaction equations of the above preparation method are as follows:

[0028] ,

[0029] Among them, R 1 、R 2 、R 3 、R 4 The definition of is the same as above. * For chiral ligands.

[0030] The beneficial effects of the present invention are:

[0031] In the prior art, reactions catalyzed by iridium (I) and chiral phosphine ligands can only achieve asymmetric nucleophilic allylation reactions, which usually require the introduction of a relatively active leaving group into the substrate. The present invention studies the activation of carbon-hydrogen bonds, which are more abundant and inert in organic compounds. It creatively uses a catalytic system of iridium (I) and chiral phosphine ligands to achieve a more difficult carbon-hydrogen bond activation reaction, successfully preparing lipid-chain-substituted biphenyl-type or phenylpyrrole-type chiral monophosphine ligands.

[0032] The present invention provides a synthetic route for lipid chain-substituted biphenyl-type or phenylpyrrole-type chiral monophosphine ligands. The raw materials are cheap and readily available, the unit operations are simple, the equipment requirements are low, and the method is suitable for rapidly constructing a novel monophosphine ligand library.

[0033] Additional aspects and advantages of the present invention will be set forth in part in the description which follows and, in part, will be obvious from the description which follows, or may be learned by practice of the present invention. DETAILED DESCRIPTION

[0034] The following are specific embodiments of the present invention, which further describe the technical solutions of the present invention, but the present invention is not limited to these embodiments.

[0035] Example 1 Synthesis of (R,E)-(2-(2-(but-2-en-2-yl)naphthalen-1-yl)phenyl)diphenylphosphine

[0036] In a 25 mL dry Schlenk tube with a stir bar, (1,5-cyclooctadienyl)iridium(I) chloride dimer (3.4 mg, 0.01 mmol, 0.05 equiv) and (R)-N-dimethyl-[(S)-1,1'-spiroindane-7,7'-diyl]phosphoramidite (7.3 mg, 0.022 mmol, 0.11 equiv) were added to 2.0 mL of toluene under Ar. The resulting mixed solution was stirred at room temperature for 1 h. Then, (2-(naphthalen-1-yl)phenyl)diphenylphosphine (77.6 mg, 0.2 mmol) and 2-butyne (54.0 mg, 1.0 mmol) were added under argon. The resulting mixture was stirred at 70°C or 90°C for 72 hours. After cooling to room temperature, the solvent was evaporated under reduced pressure. The product was separated by 300-400 mesh silica gel chromatography column with petroleum ether: dichloromethane = 10:1 as the eluent and dried in vacuo to obtain the product with a yield of 82% and an enantiomeric excess of 97%. 1 H NMR (400 MHz, CDCl3)δ 7.81 (d, J = 8.5 Hz,1H), 7.77 (d, J = 7.6 Hz, 1H), 7.41 – 7.32 (m, 4H), 7.32 – 7.27 (m, 2H), 7.24(m, 3H), 7.17 – 7.11 (m, 3H), 7.10 – 7.05 (m, 2H), 7.02 – 6.92 (m, 4H), 5.37(qd, J = 6.7, 1.6 Hz, 1H), 1.59 (s, 3H), 1.41 (d, J = 6.3 Hz, 3H); 13 C NMR (101MHz, CDCl3)δ 146.4 (d, J = 35.0 Hz), 142.3 (d, J= 1.8 Hz), 138.3 (d, J = 13.2 Hz),138.1 (d, J = 5.0 Hz), 137.9 (d, J = 2.7 Hz), 136.5, 136.0 (d, J = 7.3 Hz), 135.1(d, J = 3.2 Hz), 133.8 (d, J = 21.3 Hz), 133.0 (d, J = 2.3 Hz), 132.9 (d, J = 18.2Hz), 131.92, 131.85 (d, J = 6.4 Hz), 128.3 (d, J = 17.3 Hz), 128.1 (d, J = 5.4Hz), 128.0 (d, J = 7.3 Hz), 127.6 (d, J = 5.0 Hz), 127.4 (d, J = 16.3 Hz), 127.0(d, J = 36.8 Hz), 126.3 (d, J = 2.3 Hz), 125.3, 124.8, 17.7 (d, J = 2.3 Hz), 13.8; 31 P NMR (162 MHz, CDCl3)δ -15.66.

[0037] Example 2 Synthesis of (R,E)-(2-(2-(but-2-en-2-yl)naphthalen-1-yl)-4-methylphenyl)diphenylphosphine

[0038] In a 25.0 mL dry Schlenk tube with a stir bar, (1,5-cyclooctadiene)iridium(I) chloride dimer (3.4 mg, 0.01 mmol, 0.05 equiv) and (R)- N4-Dimethyl-[(S)-1,1'-spirodihydroindane-7,7'-diyl]phosphoramidite (7.3 mg, 0.022 mmol, 0.11 equivalents). The resulting mixed solution was stirred at room temperature for 1 hour. Then, (4-methyl-2-(naphthalen-1-yl)phenyl)diphenylphosphine (80.4 mg, 0.2 mmol) and 2-butyne (54.0 mg, 1.0 mmol) were added under argon. The resulting mixture was stirred at 70°C or 90°C for 72 hours. After cooling to room temperature, the solvent was evaporated under reduced pressure. The product was separated by chromatography on a 300-400 mesh silica gel column with petroleum ether:dichloromethane (10:1) as the eluent and dried under vacuum to obtain the product in a yield of 78% with an enantiomeric excess of 97%. 1 H NMR (500 MHz, CDCl3)δ 7.87 (d, J= 8.5 Hz, 1H), 7.84 (d, J = 8.1 Hz, 1H), 7.41 (d, J = 8.4 Hz, 1H), 7.37 –7.28 (m, 5H), 7.25 – 7.17 (m, 5H), 7.15 (td, J = 7.2, 1.5 Hz, 2H), 7.11 –7.01 (m, 4H), 5.41 (qd, J = 6.9, 1.6 Hz, 1H), 2.42 (s, 3H), 1.65 (s, 3H),1.46 (d, J = 7.1 Hz, 3H); 13 C NMR (126 MHz, CDCl3)δ 146.5 (d, J = 35.5 Hz),142.2, 138.6 (d, J = 13.1 Hz), 138.3, 136.5, 136.2 (d, J = 6.7 Hz), 135.2 (d, J =2.9 Hz), 134.3 (d, J = 10.1 Hz), 133.6 (d, J = 20.8 Hz), 133.1, 132.8 (d, J = 17.8Hz), 132.5 (d, J = 6.7 Hz), 131.9, 128.2 (d, J = 36.9 Hz), 128.01 , 127.97 ,127.91 , 127.51 , 127.46 , 127.1 (d, J = 40.1 Hz), 126.1, 125.0 (d,J = 59.7 Hz),21.3, 17.8, 13.8; 31 P NMR (202 MHz, CDCl3)δ -16.80.

[0039] Example 3 Synthesis of (R,E)-(2-(2-(but-2-en-2-yl)naphthalen-1-yl)-5-methylphenyl)diphenylphosphine

[0040] In a 25.0 mL dry Schlenk tube with a stir bar, (1,5-cyclooctadiene)iridium(I) chloride dimer (3.4 mg, 0.01 mmol, 0.05 equiv) and (R)- N 5-Dimethyl-[(S)-1,1'-spirodihydroindane-7,7'-diyl]phosphoramidite (7.3 mg, 0.022 mmol, 0.11 equivalents). The resulting mixed solution was stirred at room temperature for 1 hour. Then, (5-methyl-2-(naphthalen-1-yl)phenyl)diphenylphosphine (80.4 mg, 0.2 mmol) and 2-butyne (54.0 mg, 1.0 mmol) were added under argon. The resulting mixture was stirred at 70°C for 72 hours. After cooling to room temperature, the solvent was evaporated under reduced pressure. The product was separated by chromatography on a 300-400 mesh silica gel column with petroleum ether:dichloromethane (10:1) as the eluent and dried under vacuum to obtain the product in a 90% yield with an enantiomeric excess of 99%. 1 H NMR (400 MHz, CDCl3) δ 7.81 (d, J = 8.4Hz, 1H), 7.77 (d, J = 8.2 Hz, 1H), 7.35 (d, J = 8.4 Hz, 1H), 7.31 – 7.27 (m, 1H), 7.27 – 7.23 (m, 3H), 7.22 – 7.19 (m, 2H), 7.19 – 7.15 (m, 2H), 7.15 – 7.12(m, 2H), 7.12 – 7.07 (m, 2H), 7.03 – 7.00 (m, 1H), 7.00 – 6.95 (m, 3H), 5.36(qd, J = 6.8, 1.5 Hz, 1H), 2.33 (s, 3H), 1.59 (t, J = 1.3 Hz, 3H), 1.43 – 1.40(m, 3H); 13C NMR (101 MHz, CDCl3)δ 143.5 (d, J = 35.4 Hz), 142.5 (d, J = 1.8 Hz),138.5 (d, J = 13.6 Hz), 138.3 (d, J = 14.1 Hz), 137.5 (d, J = 11.4 Hz), 136.8,136.7, 136.1 (d, J = 6.8 Hz), 135.4 (d, J = 2.7 Hz), 133.8 (d, J = 21.3 Hz), 133.3(d, J = 1.8 Hz), 132.9 (d, J = 18.2 Hz), 132.0, 131.7 (d, J = 6.8 Hz), 129.4, 128.1(d, J = 5.9 Hz), 128.0, 127.9, 127.5 (d, J = 2.7 Hz), 127.4 (d, J = 17.3 Hz),126.9, 126.1 (d, J = 2.3 Hz), 125.0 (d, J = 46.3 Hz), 21.4, 17.8 (d, J = 2.3 Hz),13.8; 31 P NMR (202 MHz, CDCl3)δ -16.80.

[0041] Example 4 Synthesis of (R,E)-(2-(2-(but-2-en-2-yl)-4-methylnaphthalen-1-yl)phenyl)diphenylphosphine

[0042] In a 25.0 mL dry Schlenk tube with a stir bar, (1,5-cyclooctadiene)iridium(I) chloride dimer (3.4 mg, 0.01 mmol, 0.05 equiv) and (R)- N1,1'-Dimethyl-[(S)-1,1'-spirodihydroindane-7,7'-diyl]phosphoramidite (7.3 mg, 0.022 mmol, 0.11 equivalents). The resulting mixed solution was stirred at room temperature for 1 hour. Then, (2-(4-methylnaphthalen-1-yl)phenyl)diphenylphosphine (80.4 mg, 0.2 mmol) and 2-butyne (108.0 mg, 2.0 mmol) were added under argon. The resulting mixture was stirred at 70°C for 72 hours. After cooling to room temperature, the solvent was evaporated under reduced pressure. The product was separated by chromatography on a 300-400 mesh silica gel column with petroleum ether:dichloromethane (10:1) as the eluent and dried under vacuum to obtain the product in a yield of 78% with an enantiomeric excess of 99%. 1 H NMR (500 MHz, CDCl3)δ 8.01 (d, J = 8.4Hz, 1H), 7.47 – 7.42 (m, 2H), 7.41 – 7.38 (m, 2H), 7.38 – 7.34 (m, 1H), 7.33– 7.29 (m, 4H), 7.23 – 7.19 (m, 3H), 7.16 (td, J = 7.4, 6.9, 1.6 Hz, 2H), 7.10– 7.02 (m, 4H), 5.46 – 5.38 (m, 1H), 2.79 (s, 3H), 1.65 (s, 3H), 1.46 (dd, J =6.7, 1.2 Hz, 3H); 13 C NMR (126 MHz, CDCl3)δ 146.7 (d, J = 35.3 Hz), 141.8 (d, J =1.7 Hz), 138.4 (d, J = 13.3 Hz), 138.2 (d, J = 13.9 Hz), 138.0 (d, J = 11.0 Hz),136.5, 135.2 (d, J = 2.9 Hz), 134.4 (d, J = 6.9 Hz), 133.8, 133.6, 133.2 (d, J =1.7 Hz), 132.9 (d, J = 17.9 Hz), 132.1 (d, J = 6.4 Hz), 131.1, 128.4, 128.13,128.06, 128.0 (d,J = 2.3 Hz), 127.9, 127.5 (d, J = 13.9 Hz), 127.3, 126.0 (d, J =2.3 Hz), 124.8 (d, J = 37.6 Hz), 123.7, 19.6, 17.7 (d, J = 1.5 Hz), 13.8; 31 P NMR(202 MHz, CDCl3)δ -15.99.

[0043] Example 5 Synthesis of (R,E)-(2-(2-(but-2-en-2-yl)naphthalen-1-yl)-4,5-dimethylphenyl)diphenylphosphine

[0044] In a 25.0 mL dry Schlenk tube with a stir bar, (1,5-cyclooctadiene)iridium(I) chloride dimer (3.4 mg, 0.01 mmol, 0.05 equiv) and (R)- N 4-Dimethyl-[(S)-1,1'-spirodihydroindane-7,7'-diyl]phosphoramidite (7.3 mg, 0.022 mmol, 0.11 equivalents). The resulting mixed solution was stirred at room temperature for 1 hour. Then, (4,5-dimethyl-2-(naphthalen-1-yl)phenyl)diphenylphosphine (83.2 mg, 0.2 mmol) and 2-butyne (54.0 mg, 1.0 mmol) were added under argon. The resulting mixture was stirred at 70°C for 72 hours. After cooling to room temperature, the solvent was evaporated under reduced pressure. The product was separated by chromatography on a 300-400 mesh silica gel column with petroleum ether:dichloromethane (10:1) as the eluent and dried under vacuum to obtain the product in a 62% yield with an enantiomeric excess of 97%. 1 H NMR (400 MHz, CDCl3)δ 7.79 (t, J =8.1 Hz, 2H), 7.34 (d, J = 8.4 Hz, 1H), 7.30 (td, J = 5.1, 2.4 Hz, 1H), 7.30 –7.20 (m, 3H), 7.20 – 7.11 (m, 2H), 7.12 (dt, J = 2.3, 1.4 Hz, 2H), 7.10 (q, J=1.2 Hz, 1H), 7.11 – 7.05 (m, 1H), 7.07 – 7.00 (m, 2H), 7.04 – 6.95 (m, 2H),5.34 (qd, J = 6.8, 1.5 Hz, 1H), 2.27 (s, 3H), 2.24 (s, 3H), 1.59 (t, J = 1.3 Hz,3H), 1.39 (dd, J = 6.8, 1.2 Hz, 2H); 13 C NMR (101 MHz, CDCl3)δ 144.1 (d, J = 35.9Hz), 142.4 (d, J = 2.3 Hz), 138.9 (d, J = 7.7 Hz), 138.7 (d, J = 6.4 Hz), 137.2,136.7, 136.2 (d, J = 6.8 Hz), 136.1 (d, J = 3.2 Hz), 135.6, 135.4 (d, J = 3.2 Hz),134.3 (d, J = 10.0 Hz), 133.8 (d, J = 20.9 Hz), 133.6 (d, J = 20.9 Hz), 133.3 (d, J =2.3 Hz), 132.9 (d, J = 7.3 Hz), 132.8 (d, J = 17.7 Hz), 132.0, 128.0 (d, J = 2.5Hz), 127.9 (d, J = 4.1 Hz), 127.5 (d, J = 10.4 Hz), 127.3 (d, J = 3.2 Hz), 127.0,126.0 (d, J = 2.3 Hz), 125.0 (d, J = 47.2 Hz), 19.7 (d, J = 2.3 Hz), 17.8 (d, J = 1.8Hz), 13.8; 31P NMR (162 MHz, CDCl3)δ -16.69.

[0045] Example 6 Synthesis of (R,E)-(2-(2-(but-2-en-2-yl)-4-phenylnaphthalen-1-yl)phenyl)diphenylphosphine

[0046] In a 25.0 mL dry Schlenk tube with a stir bar, (1,5-cyclooctadiene)iridium(I) chloride dimer (3.4 mg, 0.01 mmol, 0.05 equiv) and (R)- N 1,1'-Dimethyl-[(S)-1,1'-spirodihydroindane-7,7'-diyl]phosphoramidite (7.3 mg, 0.022 mmol, 0.11 equivalents). The resulting mixed solution was stirred at room temperature for 1 hour. Then, diphenyl(2-(4-phenylnaphthalen-1-yl)phenyl)phosphine (92.8 mg, 0.2 mmol) and 2-butyne (54.0 mg, 1.0 mmol) were added under argon. The resulting mixture was stirred at 70°C for 72 hours. After cooling to room temperature, the solvent was evaporated under reduced pressure. The product was separated by chromatography on a 300-400 mesh silica gel column with petroleum ether:dichloromethane (10:1) as the eluent and dried under vacuum to obtain the product in a 68% yield with an enantiomeric excess of 98%. 1 H NMR (500 MHz, CDCl3)δ 7.95 (d, J = 8.2Hz, 1H), 7.69 – 7.64 (m, 2H), 7.55 (t, J = 7.7 Hz, 2H), 7.47 (td, J = 6.1, 5.0,1.9 Hz, 3H), 7.45 – 7.40 (m, 3H), 7.35 – 7.28 (m, 4H), 7.25 – 7.21 (m, 3H),7.17 (td, J = 7.3, 6.9, 1.7 Hz, 2H), 7.13 – 7.05 (m, 4H), 5.48 (qd, J = 6.7, 1.5Hz, 1H), 1.68 (s, 3H), 1.48 (d, J = 6.8 Hz, 3H); 13 C NMR (126 MHz, CDCl3)δ 146.6(d, J = 35.0 Hz), 141.9 (d, J= 2.3 Hz), 141.0, 139.7, 138.3 (d, J = 12.7 Hz),138.2 (d, J = 8.7 Hz), 138.1 (d, J = 6.4 Hz), 136.5, 135.7 (d, J = 6.4 Hz), 135.3(d, J = 2.9 Hz), 133.9 (d, J = 21.4 Hz), 133.5 (d, J = 2.9 Hz), 133.0 (d, J = 18.5Hz), 132.2 (d, J = 6.4 Hz), 130.4, 130.2, 128.5 (d, J = 7.5 Hz), 128.3, 128.2,128.2, 128.1 (d, J = 6.9 Hz), 127.8, 127.5, 127.3, 127.2, 126.6 (d, J = 2.9 Hz),125.7, 125.2, 125.0, 17.8 (d, J = 1.7 Hz), 13.9; 31 P NMR (202 MHz, CDCl3)δ -15.52.

[0047] Example 7 Synthesis of (R,E)-(2-(2-(but-2-en-2-yl)naphthalen-1-yl)-4-methoxyphenyl)diphenylphosphine

[0048] In a 25.0 mL dry Schlenk tube with a stir bar, (1,5-cyclooctadiene)iridium(I) chloride dimer (3.4 mg, 0.01 mmol, 0.05 equiv) and (R)- N4-Dimethyl-[(S)-1,1'-spirodihydroindane-7,7'-diyl]phosphoramidite (7.3 mg, 0.022 mmol, 0.11 equivalents). The resulting mixed solution was stirred at room temperature for 1 hour. Then, (4-methoxy-2-(naphthalen-1-yl)phenyl)diphenylphosphine (83.6 mg, 0.2 mmol) and 2-butyne (54.0 mg, 1.0 mmol) were added under argon. The resulting mixture was stirred at 70°C for 72 hours. After cooling to room temperature, the solvent was evaporated under reduced pressure. The product was separated by chromatography on a 300-400 mesh silica gel column with petroleum ether:dichloromethane (10:1) as the eluent and dried under vacuum to obtain the product in a yield of 76% with an enantiomeric excess of 94%. 1 H NMR (400 MHz, CDCl3)δ 7.83 (d, J =8.4 Hz, 1H), 7.80 (d, J = 8.2 Hz, 1H), 7.36 (d, J = 8.6 Hz, 1H), 7.34 – 7.28 (m,2H), 7.26 – 7.22 (m, 3H), 7.17 – 7.09 (m, 5H), 7.05 (d, J = 3.3 Hz, 2H), 7.02 –6.96 (m, 2H), 6.93 (dd, J = 8.6, 2.7 Hz, 1H), 6.86 (dd, J = 3.8, 2.7 Hz, 1H),5.41 – 5.27 (m, 1H), 3.78 (s, 3H), 1.62 (s, 3H), 1.41 (dd, J = 6.7, 1.2 Hz,3H); 13 C NMR (101 MHz, CDCl3)δ 159.7, 148.2 (d, J = 37.2 Hz), 142.1 (d, J = 2.3Hz), 139.0, 138.8, 138.7, 136.7 (d, J = 2.7 Hz), 136.4, 136.0 (d, J = 6.8 Hz),133.5 (d, J = 20.9 Hz), 132.8 (d, J = 17.7 Hz), 131.9, 128.02 (d, J = 2.3 Hz),127.98 (d,J = 1.4 Hz), 127.9, 127.6, 127.5 (d, J = 5.0 Hz), 127.2, 126.9, 126.1(d, J = 1.8 Hz), 125.4, 124.9, 116.6 (d, J = 7.3 Hz), 114.1, 55.2, 17.8 (d, J =1.8 Hz), 13.8; 31 P NMR (162 MHz, CDCl3)δ -17.81.

[0049] Example 8 Synthesis of (R,E)-(2-(2-(but-2-en-2-yl)-4-methoxynaphthalen-1-yl)phenyl)diphenylphosphine

[0050] In a 25.0 mL dry Schlenk tube with a stir bar, (1,5-cyclooctadiene)iridium(I) chloride dimer (3.4 mg, 0.01 mmol, 0.05 equiv) and (R)- N 1,1'-Dimethyl-[(S)-1,1'-spirodihydroindane-7,7'-diyl]phosphoramidite (7.3 mg, 0.022 mmol, 0.11 equivalents). The resulting mixed solution was stirred at room temperature for 1 hour. Then, (2-(4-methoxynaphthalen-1-yl)phenyl)diphenylphosphine (83.6 mg, 0.2 mmol) and 2-butyne (54.0 mg, 1.0 mmol) were added under argon. The resulting mixture was stirred at 70°C for 72 hours. After cooling to room temperature, the solvent was evaporated under reduced pressure. The product was separated by chromatography on a 300-400 mesh silica gel column using a 10:1 ratio of petroleum ether to dichloromethane. The product was dried under vacuum to obtain a yield of 71% and an enantiomeric excess of 99%. 1 H NMR (500 MHz, CDCl3)δ 8.29 (d, J = 8.3Hz, 1H), 7.47 – 7.40 (m, 3H), 7.39 – 7.33 (m, 3H), 7.33 – 7.31 (m, 2H), 7.24– 7.19 (m, 3H), 7.15 (td, J = 7.4, 1.6 Hz, 2H), 7.06 (qd, J = 8.2, 1.5 Hz, 3H),6.94 (d, J= 8.2 Hz, 1H), 6.78 (s, 1H), 5.47 (qd, J = 6.7, 1.5 Hz, 1H), 4.08 (s,3H), 1.68 (s, 3H), 1.50 – 1.47 (m, 3H); 13 C NMR (126 MHz, CDCl3)δ 154.6, 146.6(d, J = 34.7 Hz), 142.3 (d, J = 2.3 Hz), 138.6 (d, J = 6.4 Hz), 138.5 (d, J = 4.0Hz), 138.1 (d, J = 13.9 Hz), 137.0, 135.1 (d, J = 2.9 Hz), 133.8 (d, J = 20.8 Hz),132.8 (d, J = 17.9 Hz), 132.4 (d, J = 6.4 Hz), 128.3 (d, J = 26.0 Hz), 128.03 (d, J =5.5 Hz), 127.97 (d, J = 7.1 Hz), 127.5, 127.2, 126.6, 126.0 (d, J = 2.3 Hz),125.8, 124.2, 121.4, 105.2, 55.3, 17.7 (d, J = 1.7 Hz), 13.7. 17.7 (d, J = 1.7Hz); 31 P NMR (202 MHz, CDCl3)δ -15.76.

[0051] Example 9 Synthesis of (R,E)-(6-(2-(but-2-en-2-yl)naphthalen-1-yl)benzo[d][1,3]dioxol-5-yl)diphenylphosphine

[0052] In a 25.0 mL dry Schlenk tube with a stir bar, (1,5-cyclooctadiene)iridium(I) chloride dimer (3.4 mg, 0.01 mmol, 0.05 equiv) and (R)- N1,1'-Dimethyl-[(S)-1,1'-spirodihydroindane-7,7'-diyl]phosphoramidite (7.3 mg, 0.022 mmol, 0.11 equivalents). The resulting mixed solution was stirred at room temperature for 1 hour. Then, (6-(naphthalen-1-yl)benzo[d][1,3]dihydroxy-5-yl)diphenylphosphine (86.2 mg, 0.2 mmol) and 2-butyne (54.0 mg, 1.0 mmol) were added under argon. The resulting mixture was stirred at 70°C for 72 hours. After cooling to room temperature, the solvent was evaporated under reduced pressure. The product was separated by chromatography on a 300-400 mesh silica gel column with petroleum ether:dichloromethane (10:1) as the eluent and dried under vacuum to obtain the product in a yield of 78% with an enantiomeric excess of 95%. 1 H NMR (400 MHz, CDCl3)δ 7.81(t, J = 9.0 Hz, 2H), 7.35 (d, J = 8.4 Hz, 1H), 7.33 – 7.30 (m, 1H), 7.29 – 7.27(m, 1H), 7.26 – 7.23 (m, 2H), 7.21 – 7.16 (m, 1H), 7.16 – 7.11 (m, 3H), 7.11– 7.06 (m, 2H), 7.01 – 6.92 (m, 2H), 6.82 (d, J = 2.3 Hz, 1H), 6.79 (d, J = 3.7Hz, 1H), 6.05 (d, J = 1.3 Hz, 1H), 6.01 (d, J = 1.3 Hz, 1H), 5.40 – 5.31 (m, 1H), 1.63 (t, J = 1.3 Hz, 3H), 1.44 (dd, J = 6.8, 1.2 Hz, 3H); 13 C NMR (101 MHz, CDCl3)δ148.2, 147.1, 142.6 (d, J = 2.3 Hz), 141.2 (d, J = 38.1 Hz), 138.7, 138.6, 138.4,136.5, 135.7 (d, J = 7.7 Hz), 133.5 (d, J = 20.9 Hz), 132.7 (d, J= 18.2 Hz),132.0, 128.14 (d, J = 5.5 Hz), 128.06, 128.0, 127.64, 127.60, 127.1 (d, J =48.6 Hz), 126.3 (d, J = 2.3 Hz), 125.2 (d, J = 53.1 Hz), 114.0 (d, J = 2.3 Hz),111.9 (d, J = 7.3 Hz), 101.3, 17.8, 13.9; 31 P NMR (162 MHz, CDCl3)δ -15.41.

[0053] Example 10 Synthesis of (R,E)-(2-(2-(but-2-en-2-yl)naphthalen-1-yl)-5-fluorophenyl)diphenylphosphine

[0054] In a 25.0 mL dry Schlenk tube with a stir bar, (1,5-cyclooctadiene)iridium(I) chloride dimer (3.4 mg, 0.01 mmol, 0.05 equiv) and (R)- N 5-Dimethyl-[(S)-1,1'-spirodihydroindane-7,7'-diyl]phosphoramidite (7.3 mg, 0.022 mmol, 0.11 equivalents). The resulting mixed solution was stirred at room temperature for 1 hour. Then, (5-fluoro-2-(naphthalen-1-yl)phenyl)diphenylphosphine (80.4 mg, 0.2 mmol) and 2-butyne (54.0 mg, 1.0 mmol) were added under argon. The resulting mixture was stirred at 70°C for 72 hours. After cooling to room temperature, the solvent was evaporated under reduced pressure. The product was separated by chromatography on a 300-400 mesh silica gel column with petroleum ether:dichloromethane (10:1) as the eluent and dried under vacuum to obtain the product in a yield of 78% with an enantiomeric excess of 99%. 1 H NMR (400 MHz, CDCl3)δ 7.82 (d, J = 8.4Hz, 1H), 7.77 (d, J = 8.2 Hz, 1H), 7.36 (d, J= 8.4 Hz, 1H), 7.31 – 7.23 (m, 5H),7.20 – 7.14 (m, 1H), 7.14 – 7.09 (m, 4H), 7.08 – 7.02 (m, 2H), 7.01 – 6.91(m, 3H), 6.87 (d, J = 8.4 Hz, 1H), 5.37 (qd, J = 6.8, 1.6 Hz, 1H), 1.61 (s, 3H),1.46 (d, J = 6.1 Hz, 3H); 13 C NMR (101 MHz, CDCl3) δ 161.9 (d, J = 248.4 Hz),142.6, 142.0 (dd, J = 34.0, 2.9 Hz), 141.1 (dd, J = 15.6, 4.4 Hz), 137.5 (d, J =13.6 Hz), 136.9 (d, J = 14.1 Hz), 136.4, 134.8 (d, J = 6.4 Hz), 133.9 (d, J = 21.3Hz), 133.3 (t, J = 6.8 Hz), 132.8 (d, J = 18.6 Hz), 131.9, 128.6, 128.3 (d, J = 5.9Hz), 128.1 (d, J = 7.7 Hz), 127.9 (d, J = 17.3 Hz), 127.4 (d, J = 33.6 Hz), 126.6,126.4, 125.1 (d, J = 52.2 Hz), 120.9 (d, J = 22.3 Hz), 115.73 (d, J = 21.3 Hz),17.8, 13.9; 31 P NMR (162 MHz, CDCl3)δ -15.01; 19 F NMR (376 MHz, CDCl3)δ -114.59.

[0055] Example 11 Synthesis of (R,E)-(2-(2-(but-2-en-2-yl)naphthalen-1-yl)-4,5-difluorophenyl)diphenylphosphine

[0056] In a 25.0 mL dry Schlenk tube with a stir bar, (1,5-cyclooctadiene)iridium(I) chloride dimer (3.4 mg, 0.01 mmol, 0.05 equiv) and (R)- N 4-Dimethyl-[(S)-1,1'-spirodihydroindane-7,7'-diyl]phosphoramidite (7.3 mg, 0.022 mmol, 0.11 equivalents). The resulting mixed solution was stirred at room temperature for 1 hour. Then, (4,5-difluoro-2-(naphthalen-1-yl)phenyl)diphenylphosphine (84.8 mg, 0.2 mmol) and 2-butyne (54.0 mg, 1.0 mmol) were added under argon. The resulting mixture was stirred at 120°C for 72 hours. After cooling to room temperature, the solvent was evaporated under reduced pressure. The product was separated by chromatography on a 300-400 mesh silica gel column with petroleum ether:dichloromethane (10:1) as the eluent and dried under vacuum to obtain the product in a 57% yield with an enantiomeric excess of 97%. 1 H NMR (500 MHz, CDCl3)δ 7.85 (d, J =8.4 Hz, 1H), 7.80 (d, J = 8.2 Hz, 1H), 7.37 (d, J = 8.4 Hz, 1H), 7.33 – 7.28 (m,4H), 7.24 – 7.17 (m, 1H), 7.17 – 7.08 (m, 6H), 7.02 (td, J = 7.6, 6.9, 1.4 Hz,1H), 6.94 (td, J = 8.0, 1.5 Hz, 2H), 6.89 (d, J = 8.5 Hz, 1H), 5.37 (qd, J = 6.8,1.6 Hz, 1H), 1.66 (s, 3H), 1.49 (dd, J = 6.7, 1.2 Hz, 3H); 13 C NMR (126 MHz, CDCl3) δ 150.9 (dd, J = 97.4, 12.4 Hz), 148.9 (dd, J = 96.2, 12.4 Hz), 143.3(ddd,J = 36.3, 6.1, 4.2 Hz), 142.6 (d, J = 1.5 Hz), 137.4 (d, J = 13.3 Hz), 136.9(d, J = 13.9 Hz), 136.0, 135.7 - 135.5 (m), 133.8 (d, J = 21.4 Hz), 132.7 (d, J =18.5 Hz), 131.9, 128.7, 128.4 (d, J = 5.8 Hz), 128.24 (d, J = 7.5 Hz), 128.15 (d, J = 7.5 Hz), 127.4 (d, J = 65.3 Hz), 126.7 (d, J = 2.9 Hz), 126.3, 125.6, 125.3,123.1 (d, J = 16.2 Hz), 120.5 (dd, J = 15.9, 6.6 Hz), 17.9 (d, J = 2.3 Hz), 13.9; 31 PNMR (202 MHz, CDCl3)δ -16.29; 19 F NMR (471 MHz, CDCl3)δ -137.10 (d, J = 21.7 Hz,1F), -138.76 (d, J = 21.7 Hz, 1F).

[0057] Example 12 Synthesis of (R,E)-(2-(2-(but-2-en-2-yl)naphthalen-1-yl)-4-chlorophenyl)diphenylphosphine

[0058] In a 25.0 mL dry Schlenk tube with a stir bar, (1,5-cyclooctadiene)iridium(I) chloride dimer (3.4 mg, 0.01 mmol, 0.05 equiv) and (R)- N4-Dimethyl-[(S)-1,1'-spirodihydroindane-7,7'-diyl]phosphoramidite (7.3 mg, 0.022 mmol, 0.11 equivalents). The resulting mixed solution was stirred at room temperature for 1 hour. Then, (4-chloro-2-(naphthalen-1-yl)phenyl)diphenylphosphine (84.4 mg, 0.2 mmol) and 2-butyne (54.0 mg, 1.0 mmol) were added under nitrogen. The resulting mixture was stirred at 150°C for 48 hours. After cooling to room temperature, the solvent was evaporated under reduced pressure. The product was separated by chromatography on a 300-400 mesh silica gel column with petroleum ether:dichloromethane (10:1) as the eluent and dried under vacuum to obtain the product in a 65% yield with an enantiomeric excess of 97%. 1 H NMR (400 MHz, CDCl3)δ 7.83 (d, J = 8.3Hz, 1H), 7.78 (d, J = 8.5 Hz, 1H), 7.40 – 7.29 (m, 2H), 7.32 – 7.22 (m, 3H), 7.21 – 7.12 (m, 1H), 7.16 – 7.05 (m, 3H), 7.09 – 6.98 (m, 2H), 6.95 (td, J =7.7, 1.5 Hz, 3H), 5.36 (qd, J = 6.8, 1.5 Hz, 1H), 1.63 (t, J = 1.3 Hz, 3H), 1.43(dd, J = 6.9, 1.3 Hz, 2H); 13 C NMR (101 MHz, CDCl3)δ 164.0, 161.5, 149.1 (d, J =7.7 Hz), 148.7 (d, J = 7.7 Hz), 142.2 (d, J = 2.3 Hz), 138.1 (d, J = 12.7 Hz),137.8 (d, J = 13.6 Hz), 137.12 (d, J = 2.7 Hz), 137.06 (d, J = 2.3 Hz), 136.1,133.6 (d, J = 20.9 Hz), 132.8 (d, J = 17.7 Hz), 131.9, 128.3, 128.2, 128.1 (d,J =2.7 Hz), 128.0 (d, J = 7.7 Hz), 127.7 (d, J = 17.3 Hz), 127.1, 126.6 (d, J = 2.3Hz), 126.5, 125.5, 125.0, 118.7 (d, J = 6.8 Hz), 118.5 (d, J = 6.8 Hz), 114.8 (d, J = 20.9 Hz), 17.8 (d, J = 2.3 Hz), 13.9; 31 P NMR (202 MHz, CDCl3)δ -17.55.

[0059] Example 13 Synthesis of (R,E)-(2-(2-(but-2-en-2-yl)-4-chloronaphthalen-1-yl)phenyl)diphenylphosphine

[0060] In a 25.0 mL dry Schlenk tube with a stir bar, (1,5-cyclooctadiene)iridium(I) chloride dimer (3.4 mg, 0.01 mmol, 0.05 equiv) and (R)- N 1,1'-Dimethyl-[(S)-1,1'-spirodihydroindane-7,7'-diyl]phosphoramidite (7.3 mg, 0.022 mmol, 0.11 equivalents). The resulting mixed solution was stirred at room temperature for 1 hour. Then, (2-(4-chloronaphthalen-1-yl)phenyl)diphenylphosphine (84.4 mg, 0.2 mmol) and 2-butyne (54.0 mg, 1.0 mmol) were added under argon. The resulting mixture was stirred at 70°C for 72 hours. After cooling to room temperature, the solvent was evaporated under reduced pressure. The product was separated by chromatography on a 300-400 mesh silica gel column with petroleum ether:dichloromethane (10:1) as the eluent and dried under vacuum to obtain the product in an 87% yield with an enantiomeric excess of 97%. 1 H NMR (500 MHz, CDCl3)δ 8.27 (d, J = 8.4 Hz,1H), 7.55 (s, 1H), 7.47 – 7.37 (m, 4H), 7.33 – 7.29 (m, 4H), 7.23 – 7.11 (m,5H), 7.09 – 7.05 (m, 1H), 7.04 – 6.97 (m, 3H), 5.45 (qd, J= 6.8, 1.5 Hz, 1H),1.63 (s, 3H), 1.48 – 1.46 (m, 3H); 13 C NMR (126 MHz, CDCl3)δ 145.5 (d, J = 34.8Hz), 142.5 (d, J = 1.7 Hz), 138.05, 138.04 (d, J = 24.3 Hz), 137.6 (d, J = 13.3Hz), 135.6, 135.4 (d, J = 6.4 Hz), 135.1 (d, J = 2.9 Hz), 134.2 (d, J = 2.3 Hz),133.8 (d, J = 21.4 Hz), 132.8 (d, J = 18.5 Hz), 131.9 (d, J = 6.4 Hz), 131.2,129.2, 128.6, 128.3, 128.1 (d, J = 5.8 Hz), 128.0 (d, J = 7.5 Hz), 127.7 (d, J =15.6 Hz), 127.4 (d, J = 22.5 Hz), 127.1 (d, J = 2.3 Hz), 125.9 (d, J = 9.8 Hz),124.0, 17.5 (d, J = 2.3 Hz), 13.8; 31 P NMR (202 MHz, CDCl3)δ -15.72.

[0061] Example 14 Synthesis of (R,E)-(2-(2-(but-2-en-2-yl)naphthalen-1-yl)-4-(trifluoromethyl)phenyl)diphenylphosphine

[0062] In a 25.0 mL dry Schlenk tube with a stir bar, (1,5-cyclooctadiene)iridium(I) chloride dimer (3.4 mg, 0.01 mmol, 0.05 equiv) and (R)- N1,1'-Dimethyl-[(S)-1,1'-spirodihydroindane-7,7'-diyl]phosphoramidite (7.3 mg, 0.022 mmol, 0.11 equivalents). The resulting mixed solution was stirred at room temperature for 1 hour. Then, (2-(naphthalen-1-yl)-4-(trifluoromethyl)phenyl)diphenylphosphine (91.2 mg, 0.2 mmol) and 2-butyne (54.0 mg, 1.0 mmol) were added under argon. The resulting mixture was stirred at 70°C for 72 hours. After cooling to room temperature, the solvent was evaporated under reduced pressure. The product was separated by chromatography on a 300-400 mesh silica gel column with petroleum ether:dichloromethane (10:1) as the eluent and dried in vacuo to obtain the product in a 51% yield with an enantiomeric excess of 98%. 1 H NMR (500 MHz, CDCl3)δ 7.90 (d, J =8.4 Hz, 1H), 7.83 (d, J = 8.3 Hz, 1H), 7.63 (d, J = 7.6 Hz, 2H), 7.52 (d, J = 7.4Hz, 1H), 7.45 – 7.41 (m, 1H), 7.38 – 7.29 (m, 5H), 7.26 – 7.20 (m, 2H), 7.19– 7.11 (m, 4H), 7.04 – 6.97 (m, 3H), 6.86 (d, J = 8.5 Hz, 1H), 5.41 (q, J = 6.8Hz, 1H), 1.67 (s, 3H), 1.50 (d, J = 6.7 Hz, 3H); 13 C NMR (126 MHz, CDCl3)δ 146.9(d, J = 34.7 Hz), 143.5 (d, J = 15.6 Hz), 142.5, 137.3 (d, J = 13.3 Hz), 136.4 (d, J = 13.3 Hz), 136.0, 135.2 (d, J = 2.9 Hz), 134.5 (d, J = 6.4 Hz), 134.0 (d, J = 21.4Hz), 132.9 (d, J = 18.5 Hz), 132.6 (d, J= 2.3 Hz), 131.9, 130.4 (q, J = 32.4 Hz),128.7, 128.3 (d, J = 5.8 Hz), 128.24, 128.18, 128.1, 127.6, 127.1, 126.8 (d, J =2.3 Hz), 126.3, 125.6, 125.0, 123.8 (q, J = 3.5 Hz), 17.8 (d, J = 2.3 Hz), 13.8; 31 P NMR (202 MHz, CDCl3)δ -15.87; 19 F NMR (471 MHz, CDCl3)δ -62.65.

[0063] Example 15 Synthesis of (R,E)-(2-(2-(but-2-en-2-yl)naphthalen-1-yl)-5-(trifluoromethyl)phenyl)diphenylphosphine

[0064] In a 25 mL Schlenk tube, (1,5-cyclooctadienyl)iridium(I) chloride dimer (3.4 mg, 0.01 mmol, 0.05 equiv) and (R)-(+)-(3,5-dioxa-4-phosphacyclohepta[2,1-a;3,4-a']dinaphth-4-yl)-5-hydro-dibenzo[b,f]azepine (7.3 mg, 0.022 mmol, 0.11 equiv) were added to 2.0 mL of toluene in a dry 25.0 mL Schlenk tube with a stir bar under Ar. The resulting mixed solution was stirred at room temperature for 1 h. Then, (2-(naphthalen-1-yl)-5-(trifluoromethyl)phenyl)diphenylphosphine (91.2 mg, 0.2 mmol) and 2-butyne (54.0 mg, 1.0 mmol) were added under argon, and the resulting mixture was stirred at 70°C for 72 hours. After cooling to room temperature, the solvent was evaporated under reduced pressure, and the product was separated by 300-400 mesh silica gel chromatography column with petroleum ether:dichloromethane = 10:1 as the eluent. The product was dried in vacuo to obtain the product with a yield of 73% and an enantiomeric excess of 95%. 1 H NMR(500 MHz, CDCl3)δ 7.91 (d, J = 8.5 Hz, 1H), 7.85 (d, J = 8.1 Hz, 1H), 7.74 – 7.67(m, 2H), 7.49 (dd, J = 7.8, 4.1 Hz, 1H), 7.45 (d,J = 8.4 Hz, 1H), 7.38 – 7.32(m, 4H), 7.25 – 7.21 (m, 1H), 7.20 – 7.13 (m, 4H), 7.08 – 7.02 (m, 1H), 7.00(td, J = 8.0, 1.5 Hz, 2H), 6.86 (d, J = 8.4 Hz, 1H), 5.44 (qd, J = 6.7, 1.5 Hz,1H), 1.70 (t, J = 1.4 Hz, 3H), 1.52 (dd, J = 6.7, 1.4 Hz, 3H); 13 C NMR (126 MHz,CDCl3)δ 150.2 (d, J = 34.1 Hz), 142.2 (d, J = 1.7 Hz), 140.2 (d, J = 16.2 Hz),137.1 (d, J = 13.3 Hz), 136.5 (d, J = 13.9 Hz), 136.0, 134.6 (d, J = 6.4 Hz), 133.9(d, J = 21.4 Hz), 132.7 (d, J = 17.9 Hz), 132.5 (d, J = 2.3 Hz), 132.6 (d, J = 5.2Hz), 131.9, 131.3 (t, J = 3.2 Hz), 129.5 (q, J = 32.1 Hz), 128.7, 128.4 (d, J = 5.2Hz), 128.2 (d, J = 7.5 Hz), 128.1, 127.4 (d, J = 60.7 Hz), 126.8 (d, J = 2.3 Hz),126.3, 125.6, 125.01, 124.96, 124.1 (q, J = 272.6 Hz), 17.8 (d, J = 2.3 Hz),13.9; 31P NMR (202 MHz, CDCl3)δ -15.40; 19 F NMR (471 MHz, CDCl3)δ -62.30.

[0065] Example 16 Synthesis of (R,E)-(2-(4-(but-2-en-2-yl)-1,2-dihydroacenaphthen-5-yl)phenyl)diphenylphosphine

[0066] In a 25.0 mL dry Schlenk tube with a stir bar, (1,5-cyclooctadiene)iridium(I) chloride dimer (3.4 mg, 0.01 mmol, 0.05 equiv) and (R)- N 1,1'-Dimethyl-[(S)-1,1'-spirodihydroindane-7,7'-diyl]phosphoramidite (7.3 mg, 0.022 mmol, 0.11 equivalents). The resulting mixed solution was stirred at room temperature for 1 hour. Then, (2-(1,2-dihydroacenaphthen-5-yl)phenyl)diphenylphosphine (91.2 mg, 0.2 mmol) and 2-butyne (54.0 mg, 1.0 mmol) were added under argon. The resulting mixture was stirred at 70°C for 72 hours. After cooling to room temperature, the solvent was evaporated under reduced pressure. The product was separated by chromatography on a 300-400 mesh silica gel column with petroleum ether:dichloromethane (10:1) as the eluent and dried under vacuum to obtain the product in a yield of 76% with an enantiomeric excess of 97%. 1 H NMR (500 MHz, CDCl3)δ 7.46 – 7.41 (m,2H), 7.40 – 7.34 (m, 1H), 7.34 – 7.30 (m, 3H), 7.25 – 7.21 (m, 4H), 7.19 (d, J = 6.1 Hz, 2H), 7.17 – 7.13 (m, 2H), 7.09 (t, J = 7.2 Hz, 2H), 6.80 (d, J = 8.2Hz, 1H), 5.38 (q, J = 6.9 Hz, 1H), 3.47 (t, J = 9.1 Hz, 4H), 1.65 (s, 3H), 1.43(d, J = 6.7 Hz, 3H); 13 C NMR (126 MHz, CDCl3) δ 146.5 (d, J = 35.3 Hz), 145.3 (d, J=14.4 Hz), 144.2 (d, J = 2.3 Hz), 138.7 (d, J = 14.4 Hz), 138.3 (d, J = 13.3 Hz),137.7, 137.6 (d, J = 10.4 Hz), 136.9, 135.3 (d, J = 2.9 Hz), 133.5 (d, J = 20.8Hz), 133.0 (d, J = 18.5 Hz), 132.0 (d, J = 6.4 Hz), 131.4 (d, J = 2.3 Hz), 128.5,128.1, 128.00, 127.95 (d, J = 6.9 Hz), 127.6, 127.4, 127.1, 126.1 (d, J = 2.3Hz), 121.8, 120.6, 118.5, 30.5, 30.2, 17.9, 13.8; 31 P NMR (202 MHz, CDCl3)δ -16.06.

[0067] Example 17 Synthesis of (S,E)-(2-(10-(but-2-en-2-yl)phenanthrene-9-yl)phenyl)diphenylphosphine

[0068] In a 25.0 mL dry Schlenk tube with a stir bar, (1,5-cyclooctadiene)iridium(I) chloride dimer (3.4 mg, 0.01 mmol, 0.05 equiv) and (R)- N 1,1'-Dimethyl-[(S)-1,1'-spirodihydroindane-7,7'-diyl]phosphoramidite (7.3 mg, 0.022 mmol, 0.11 equivalents). The resulting mixed solution was stirred at room temperature for 1 hour. Then, (2-(phenanthren-9-yl)phenyl)diphenylphosphine (87.6 mg, 0.2 mmol) and 2-butyne (54.0 mg, 1.0 mmol) were added under argon. The resulting mixture was stirred at 70°C for 72 hours. After cooling to room temperature, the solvent was evaporated under reduced pressure. The product was separated by chromatography on a 300-400 mesh silica gel column with petroleum ether:dichloromethane (10:1) as the eluent and dried under vacuum to obtain the product in a 43% yield with an enantiomeric excess of 97%. 1H NMR (500 MHz, CDCl3)δ 8.17 (d, J = 7.6 Hz, 1H),8.13 – 8.08 (m, 3H), 8.08 – 8.04 (m, 1H), 7.96 (t, J = 7.6 Hz, 1H), 7.59 (d, J =9.3 Hz, 1H), 7.52 – 7.43 (m, 4H), 7.34 – 7.28 (m, 3H), 7.24 – 7.15 (m, 4H),7.07 (t, J = 7.6 Hz, 2H), 7.01 – 6.94 (m, 2H), 5.66 – 5.54 (m, 1H), 1.76 (s,3H), 1.57 (dd, J = 6.7, 1.4 Hz, 3H); 13 C NMR (126 MHz, CDCl3)δ 146.7 (d, J = 34.7Hz), 143.5, 138.6 (d, J = 11.6 Hz), 138.4 (d, J = 13.3 Hz), 137.6 (d, J = 13.9 Hz),137.2, 135.3 (d, J = 6.4 Hz), 135.0 (d, J = 2.9 Hz), 134.0 (d, J = 21.4 Hz), 132.9(d, J = 17.9 Hz), 132.2 (d, J = 6.4 Hz), 131.3, 130.7 (d, J = 22.5 Hz), 130.0 (d, J =2.9 Hz), 128.4 (d, J = 7.5 Hz), 128.2 (d, J = 5.2 Hz), 128.1 (d, J = 2.9 Hz), 127.7(d, J = 8.7 Hz), 127.4 (d, J = 32.4 Hz), 127.0 (d, J= 2.9 Hz), 126.6, 126.1, 125.5(d, J = 31.2 Hz), 124.8 (d, J = 19.7 Hz), 124.6, 123.4, 18.3 (d, J = 1.2 Hz), 14.1; 31 P NMR (202 MHz, CDCl3)δ -15.50.

[0069] Example 18 Synthesis of (R,E)-(2-(2-(but-2-en-2-yl)pyrene-1-yl)phenyl)diphenylphosphine

[0070] In a 25 mL dry Schlenk tube with a stir bar, (1,5-cyclooctadienyl)iridium(I) chloride dimer (3.4 mg, 0.01 mmol, 0.05 equiv) and (3aR,8aR)-(2,2-dimethyl-4,4,8,8-tetraphenyl-tetrahydro-[1,3]dioxazolo[4,5-e][1,3,2]dioxaphosphin-6-yl)dimethylamine (7.3 mg, 0.022 mmol, 0.11 equiv) were added to 2.0 mL of toluene under Ar. The resulting mixture was stirred at room temperature for 1 h. Diphenyl(2-(pyrene-1-yl)phenyl)phosphine (92.4 mg, 0.2 mmol) and 2-butyne (54.0 mg, 1.0 mmol) were then added under argon. The resulting mixture was stirred at 70°C for 72 hours. After cooling to room temperature, the solvent was evaporated under reduced pressure. The product was separated by 300-400 mesh silica gel chromatography column with petroleum ether:dichloromethane = 10:1 as the eluent and dried in vacuo to obtain the product in a yield of 59% and an enantiomeric excess of 99%. 1HNMR (500 MHz, CDCl3)δ 8.21 – 8.17 (m, 2H), 8.16 – 8.09 (m, 3H), 8.00 (t, J =7.6 Hz, 1H), 7.65 (d, J = 9.3 Hz, 1H), 7.58 – 7.55 (m, 1H), 7.54 – 7.50 (m,3H), 7.38 – 7.33 (m, 3H), 7.31 – 7.27 (m, 2H), 7.25 – 7.20 (m, 2H), 7.12 (td,J = 7.6, 1.7 Hz, 2H), 7.05 (td, J = 7.9, 1.5 Hz, 2H), 5.68 (qd, J = 6.7, 1.5Hz, 1H), 1.83 (s, 3H), 1.64 (dd, J = 6.8, 1.3 Hz, 3H).; 13 C NMR (101 MHz,CDCl3)δ 146.6 (d, J = 35.0 Hz), 143.5, 138.6 (d, J = 11.8 Hz), 138.4 (d, J = 13.2Hz), 137.6 (d, J = 14.1 Hz), 137.1, 135.2 (d, J = 5.9 Hz), 134.9 (d, J = 2.7 Hz),134.0 (d, J = 21.3 Hz), 132.8 (d, J = 18.2 Hz), 132.2 (d, J = 5.9 Hz), 131.2, 130.7(d, J = 18.2 Hz), 130.0 (d, J = 2.7 Hz), 128.3 (d, J = 5.9 Hz), 128.1 (d, J = 6.4Hz), 128.0 , 127.6 (d, J = 7.3 Hz), 127.5, 127.2, 126.9 (d, J = 2.7 Hz), 126.5,126.0, 125.4 (d, J = 24.5 Hz), 124.7 (d,J = 15.9 Hz), 124.6, 123.3, 18.2, 14.0; 31 P NMR (202 MHz, CDCl3)δ -15.42.

[0071] Example 19 Synthesis of (R,E)-(2-(but-2-en-2-yl)-[1,2'-binaphthyl]-3'-yl)diphenylphosphine

[0072] In a 25.0 mL dry Schlenk tube with a stir bar, bicyclooctenyliridium(I) chloride dimer (3.4 mg, 0.01 mmol, 0.05 equiv) and (R)- N 1,1'-Dimethyl-[(S)-1,1'-spirodihydroindane-7,7'-diyl]phosphoramidite (7.3 mg, 0.022 mmol, 0.11 equivalents). The resulting mixed solution was stirred at room temperature for 1 hour. Then, [1,2'-binaphthyl]-3'-diphenylphosphine (87.6 mg, 0.2 mmol) and 2-butyne (54.0 mg, 1.0 mmol) were added under argon. The resulting mixture was stirred at 70°C for 72 hours. After cooling to room temperature, the solvent was evaporated under reduced pressure. The product was separated by chromatography on a 300-400 mesh silica gel column with petroleum ether:dichloromethane (10:1) as the eluent and dried under vacuum to obtain the product in a yield of 74% with an enantiomeric excess of 99%. 1 H NMR (500 MHz, CDCl3)δ 8.21 – 8.17 (m, 2H), 8.16– 8.09 (m, 3H), 8.00 (t, J = 7.6 Hz, 1H), 7.65 (d, J = 9.3 Hz, 1H), 7.58 –7.55 (m, 1H), 7.54 – 7.50 (m, 3H), 7.38 – 7.33 (m, 3H), 7.31 – 7.27 (m, 2H), 7.25 – 7.20 (m, 2H), 7.12 (td, J = 7.6, 1.7 Hz, 2H), 7.05 (td, J = 7.9, 1.5Hz, 2H), 5.68 (qd, J = 6.7, 1.5 Hz, 1H), 1.83 (s, 3H), 1.64 (dd, J = 6.8, 1.3Hz, 3H).; 13 C NMR (101 MHz, CDCl3)δ 146.6 (d, J = 35.0 Hz), 143.5, 138.6 (d,J =11.8 Hz), 138.4 (d, J = 13.2 Hz), 137.6 (d, J = 14.1 Hz), 137.1, 135.2 (d, J = 5.9Hz), 134.9 (d, J = 2.7 Hz), 134.0 (d, J = 21.3 Hz), 132.8 (d, J = 18.2 Hz), 132.2(d, J = 5.9 Hz), 131.2, 130.7 (d, J = 18.2 Hz), 130.0 (d, J = 2.7 Hz), 128.3 (d, J =5.9 Hz), 128.1 (d, J = 6.4 Hz), 128.0 , 127.6 (d, J = 7.3 Hz), 127.5, 127.2,126.9 (d, J = 2.7 Hz), 126.5, 126.0, 125.4 (d, J = 24.5 Hz), 124.7 (d, J = 15.9Hz), 124.6, 123.3, 18.2, 14.0; 31 P NMR (202 MHz, CDCl3)δ -15.42.

[0073] Example 20 Synthesis of (S,E)-3-(but-2-en-2-yl)-4-(2-(diphenylphosphino)phenyl)quinoline

[0074] In a 25.0 mL dry Schlenk tube with a stir bar, (1,5-cyclooctadiene)iridium(I) chloride dimer (3.4 mg, 0.01 mmol, 0.05 equiv) and (R)- N4-Dimethyl-[(S)-1,1'-spirodihydroindane-7,7'-diyl]phosphoramidite (7.3 mg, 0.022 mmol, 0.11 equivalents). The resulting mixed solution was stirred at room temperature for 1 hour. Then, 4-(2-(diphenylphosphino)phenyl)quinoline (77.8 mg, 0.2 mmol) and 2-butyne (54.0 mg, 1.0 mmol) were added under argon. The resulting mixture was stirred at 70°C for 72 hours. After cooling to room temperature, the solvent was evaporated under reduced pressure. The product was separated by chromatography on a 300-400 mesh silica gel column with petroleum ether:dichloromethane (10:1) as the eluent and dried in vacuo to obtain the product in a 49% yield with an enantiomeric excess of 97%. 1 H NMR (500 MHz, CDCl3)δ 8.82 (s, 1H), 8.09 (d, J= 8.3 Hz, 1H), 7.54 (m, 1H), 7.48 – 7.42 (m, 1H), 7.40 (m, 2H), 7.29 (m, 4H),7.21 – 7.16 (m, 1H), 7.16 – 7.06 (m, 5H), 7.01 – 6.94 (m, 3H), 5.50 (qd, J =6.7, 1.5 Hz, 1H); 13 C NMR (126 MHz, CDCl3)δ 151.2, 146.6, 144.2 (d, J = 6.5 Hz),143.6 (d, J = 34.7 Hz), 137.5 (d, J = 12.7 Hz), 137.3 (d, J = 13.9 Hz), 137.2 (d, J =11.0 Hz), 137.1, 135.2 (d, J = 2.9 Hz), 133.7 (d, J = 20.8 Hz), 133.3, 132.8 (d, J = 18.5 Hz), 130.8 (d, J = 6.4 Hz), 128.9, 128.6, 128.4, 128.4 (d, J = 2.3 Hz),128.23, 128.19, 128.14, 128.01 (d, J = 19.1 Hz), 127.7 (d, J = 1.7 Hz), 126.5,125.9, 17.4 (d,J = 1.7 Hz), 14.0; 31 P NMR (202 MHz, CDCl3)δ -15.48.

[0075] Example 21 Synthesis of (R,E)-(2-(2-(but-2-en-2-yl)dibenzo[b,d]furan-1-yl)phenyl)diphenylphosphine

[0076] In a 25.0 mL dry Schlenk tube with a stir bar, (1,5-cyclooctadiene)iridium(I) chloride dimer (3.4 mg, 0.01 mmol, 0.05 equiv) and (R)- N 1,1'-Dimethyl-[(S)-1,1'-spirodihydroindane-7,7'-diyl]phosphoramidite (7.3 mg, 0.022 mmol, 0.11 equivalents). The resulting mixed solution was stirred at room temperature for 1 hour. Then, (2-(dibenzo[b,d]furan-1-yl)phenyl)diphenylphosphine (85.6 mg, 0.2 mmol) and 2-butyne (54.0 mg, 1.0 mmol) were added under argon. The resulting mixture was stirred at 70°C for 72 hours. After cooling to room temperature, the solvent was evaporated under reduced pressure. The product was separated by chromatography on a 300-400 mesh silica gel column with petroleum ether:dichloromethane (10:1) as the eluent and dried under vacuum to obtain the product in an 84% yield with an enantiomeric excess of 98%. 1 H NMR (500 MHz, CDCl3)δ 7.55 (d, J =8.4 Hz, 1H), 7.50 – 7.42 (m, 5H), 7.35 (d, J = 8.4 Hz, 1H), 7.31 (t, J = 6.0 Hz,3H), 7.28 (d, J = 7.9 Hz, 1H), 7.21 (td, J = 7.0, 2.2 Hz, 2H), 7.00 (t, J = 7.2 Hz,1H), 6.94 – 6.83 (m, 5H), 6.24 (d, J = 7.8 Hz, 1H), 5.36 (q, J = 6.7 Hz, 1H),1.63 (s, 3H), 1.41 (d, J = 6.9 Hz, 3H); 13C NMR (126 MHz, CDCl3)δ 156.4, 154.3,145.7 (d, J = 34.7 Hz), 140.0 (d, J = 2.3 Hz), 137.7, 137.6, 137.4 (d, J = 12.7Hz), 135.4, 135.1 (d, J = 2.9 Hz), 134.3 (d, J = 6.9 Hz), 133.7 (d, J = 21.4 Hz),133.0 (d, J = 18.5 Hz), 130.8 (d, J = 5.8 Hz), 128.8, 128.1 (d, J = 5.2 Hz), 128.0(d, J = 17.9 Hz), 127.8 (d, J = 3.4 Hz), 127.7, 126.6 (d, J = 2.3 Hz), 126.3,124.5, 123.5, 122.0 (d, J = 38.1 Hz), 110.7 (d, J = 76.3 Hz), 18.1 (d, J = 2.3 Hz),13.9; 31 P NMR (202 MHz, CDCl3)δ -15.33.

[0077] Example 22 Synthesis of (R,E)-1-(2-(but-2-en-2-yl)naphthalen-1-yl)-2-(diphenylphosphino)pyrrole

[0078] In a 25.0 mL dry Schlenk tube with a stir bar, bis(1,5-cyclooctadiene)-iridium trifluoromethanesulfonate (3.4 mg, 0.01 mmol, 0.05 equiv) and (R)- N2-Dimethyl-[(S)-1,1'-spirodihydroindane-7,7'-diyl]phosphoramidite (7.3 mg, 0.022 mmol, 0.11 equivalents). The resulting mixed solution was stirred at room temperature for 1 hour. 2-(Diphenylphosphino)-1-(naphthalen-1-yl)pyrrole (75.4 mg, 0.2 mmol) and 2-butyne (54.0 mg, 1.0 mmol) were then added under argon. The resulting mixture was stirred at 70°C for 72 hours. After cooling to room temperature, the solvent was evaporated under reduced pressure. The product was separated by chromatography on a 300-400 mesh silica gel column using a 10:1 ratio of petroleum ether to dichloromethane. The product was dried under vacuum to obtain a 69% yield with an enantiomeric excess of 96%. 1 H NMR (500 MHz, CDCl3)δ 7.87(dd, J = 18.8, 8.3 Hz, 2H), 7.47 – 7.41 (m, 2H), 7.39 – 7.35 (m, 2H), 7.32 (d, J = 7.0 Hz, 3H), 7.25 – 7.14 (m, 6H), 7.04 (s, 1H), 6.97 (d, J = 8.5 Hz, 1H),6.46 (d, J = 26.2 Hz, 2H), 5.49 (q, J = 6.9 Hz, 1H), 1.59 (s, 3H), 1.44 (d, J = 6.9Hz, 3H); 13 C NMR (126 MHz, CDCl3)δ 141.6, 138.8 (d, J = 6.9 Hz), 137.8 (d, J = 6.4Hz), 134.2, 133.1 (d, J = 20.2 Hz), 132.9 (d, J = 19.1 Hz), 132.5, 132.3 (d, J =2.3 Hz), 131.0 (d, J = 3.5 Hz), 128.5, 127.99 (d, J = 3.5 Hz), 127.96, 127.9 (d, J = 6.4 Hz), 127.3 (d, J = 26.5 Hz), 126.7 (d, J= 17.3 Hz), 125.7, 123.5, 118.9(d, J = 3.5 Hz), 109.7, 16.4, 13.8; 31 P NMR (202 MHz, CDCl3)δ -33.62.

[0079] Example 23 Synthesis of (R,E)-(2-(2-(but-2-en-2-yl)naphthalen-1-yl)phenyl)bis(4-fluorophenyl)phosphine

[0080] In a 25.0 mL dry Schlenk tube with a stir bar, (1,5-cyclooctadiene)iridium(I) chloride dimer (3.4 mg, 0.01 mmol, 0.05 equiv) and (R)- N 1,1'-Dimethyl-[(S)-1,1'-spirodihydroindane-7,7'-diyl]phosphoramidite (7.3 mg, 0.022 mmol, 0.11 equivalents). The resulting mixed solution was stirred at room temperature for 1 hour. Bis(4-fluorophenyl)(2-(naphthalen-1-yl)phenyl)phosphine (84.8 mg, 0.2 mmol) and 2-butyne (54.0 mg, 1.0 mmol) were then added under argon. The resulting mixture was stirred at 70°C for 72 hours. After cooling to room temperature, the solvent was evaporated under reduced pressure and the product was separated by chromatography on a 300-400 mesh silica gel column using a 10:1 ratio of petroleum ether to dichloromethane. The product was dried under vacuum to obtain a 52% yield with an enantiomeric excess of 97%. 1 H NMR (500 MHz, CDCl3)δ 7.85 (d, J = 8.4Hz, 1H), 7.80 (d, J = 8.2 Hz, 1H), 7.45 (t, J = 7.4 Hz, 1H), 7.39 (t, J = 8.4 Hz,2H), 7.36 – 7.28 (m, 3H), 7.14 – 7.05 (m, 2H), 7.04 – 6.97 (m, 3H), 6.92 (q, J = 7.4, 6.6 Hz, 2H), 6.87 (d, J = 8.5 Hz, 1H), 6.81 (t, J = 8.6 Hz, 2H), 5.41 (q, J = 6.8 Hz, 1H), 1.64 (s, 3H), 1.48 (d, J= 6.7 Hz, 3H); 13 C NMR (126 MHz, CDCl3)δ163.9 (d, J = 48.6 Hz), 162.0 (d, J = 48.0 Hz), 146.2 (d, J = 34.1 Hz), 142.3 (d, J =2.3 Hz), 137.9 (d, J = 11.6 Hz), 136.5, 135.8 (d, J = 8.1 Hz), 135.6 (d, J = 7.5Hz), 134.6 (d, J = 7.5 Hz), 134.5 (d, J = 7.5 Hz), 134.3 (d, J = 2.9 Hz), 133.5(dd, J = 13.6, 3.8 Hz), 133.0 (dd, J = 14.0, 3.0 Hz), 132.9 (d, J = 2.3 Hz), 132.0(d, J = 6.4 Hz), 131.9, 128.6, 127.7, 127.6, 127.2, 126.6, 126.2 (d, J = 2.9 Hz),125.1 (d, J = 54.9 Hz), 115.4 (dd, J = 16.5, 4.3 Hz), 115.3, 115.2 (d, J = 8.1 Hz),17.7 (d, J = 2.3 Hz), 13.9; 19 F NMR (471 MHz, CDCl3)δ -112.90 (d, J = 4.3 Hz, 1F), -113.78 (d, J = 5.2 Hz, 1F); 31 P NMR (202 MHz, CDCl3)δ -17.63.

[0081] Example 24 Synthesis of (R,E)-(2-(2-(but-2-en-2-yl)naphthalen-1-yl)phenyl)di(thiophen-2-yl)phosphine

[0082] In a 25.0 mL dry Schlenk tube with a stir bar, (1,5-cyclooctadiene)iridium(I) chloride dimer (3.4 mg, 0.01 mmol, 0.05 equiv) and (R)- N 1,1'-Dimethyl-[(S)-1,1'-spirodihydroindane-7,7'-diyl]phosphoramidite (7.3 mg, 0.022 mmol, 0.11 equivalents). The resulting mixed solution was stirred at room temperature for 1 hour. Then, (2-(naphthalen-1-yl)phenyl)di(thiophen-2-yl)phosphine (80.0 mg, 0.2 mmol) and 2-butyne (54.0 mg, 1.0 mmol) were added under argon. The resulting mixture was stirred at 70°C for 72 hours. After cooling to room temperature, the solvent was evaporated under reduced pressure. The product was separated by chromatography on a 300-400 mesh silica gel column with petroleum ether:dichloromethane (10:1) as the eluent and dried under vacuum to obtain the product in a yield of 74% with an enantiomeric excess of 95%. 1 H NMR (500 MHz, CDCl3)δ 7.87 (d, J = 8.4Hz, 1H), 7.82 (d, J = 8.2 Hz, 1H), 7.73 (dt, J = 7.0, 3.9 Hz, 1H), 7.56 – 7.51(m, 1H), 7.49 – 7.41 (m, 2H), 7.41 (d, J = 5.5 Hz, 1H), 7.36 – 7.29 (m, 1H), 7.32 – 7.25 (m, 1H), 7.11 – 7.05 (m, 2H), 7.08 – 7.01 (m, 1H), 7.00 (d, J = 8.4Hz, 1H), 6.86 – 6.80 (m, 1H), 6.74 – 6.68 (m, 1H), 5.44 (qd, J = 6.8, 1.5 Hz,1H), 1.65 (s, 3H), 1.50 (d, J = 6.7 Hz, 3H); 13 C NMR (126 MHz, CDCl3)δ 145.0 (d, J = 37.0 Hz), 142.4, 139.2 (d, J = 26.0 Hz), 138.8 (d, J = 17.3 Hz), 138.7 (d, J=2.9 Hz), 136.5, 135.5 (d, J = 7.5 Hz), 135.1 (d, J = 27.7 Hz), 134.5 (d, J = 22.5Hz), 133.6 (d, J = 2.9 Hz), 133.0 (d, J = 2.3 Hz), 131.8, 131.5 (d, J = 6.4 Hz),131.2, 130.8 (d, J = 2.3 Hz), 128.9, 127.8 (d, J = 6.4 Hz), 127.7, 127.5 (d, J =9.8 Hz), 127.4 (d, J = 8.1 Hz), 127.2, 126.4, 126.2 (d, J = 2.9 Hz), 125.4,124.8, 17.7 (d, J = 2.3 Hz), 13.8; 31 P NMR (202 MHz, CDCl3)δ -41.90.

[0083] Example 25 Synthesis of (R,E)-(2-(2-(hexyl-3-en-3-yl)naphthalen-1-yl)phenyl)diphenylphosphine

[0084] In a 25.0 mL dry Schlenk tube with a stir bar, (1,5-cyclooctadiene)iridium(I) chloride dimer (3.4 mg, 0.01 mmol, 0.05 equiv) and (R)- N 2-Dimethyl-[(S)-1,1'-spirodihydroindane-7,7'-diyl]phosphoramidite (7.3 mg, 0.022 mmol, 0.11 equivalents). The resulting mixed solution was stirred at room temperature for 1 hour. Then, (2-(naphthalen-1-yl)phenyl)diphenylphosphine (77.6 mg, 0.2 mmol) and 3-hexyne (82.0 mg, 1.0 mmol) were added under argon. The resulting mixture was stirred at 70°C for 72 hours. After cooling to room temperature, the solvent was evaporated under reduced pressure. The product was separated by chromatography on a 300-400 mesh silica gel column with petroleum ether:dichloromethane (10:1) as the eluent and dried under vacuum to obtain the product in a 99% yield with an enantiomeric excess of 91%. 1H NMR (500 MHz, CDCl3)δ 7.86 (d, J = 8.4 Hz, 1H),7.81 (d, J = 7.9 Hz, 1H), 7.46 – 7.42 (m, 2H), 7.42 – 7.37 (m, 2H), 7.35 – 7.31(m, 1H), 7.31 – 7.26 (m, 4H), 7.23 – 7.16 (m, 3H), 7.13 (td, J = 7.4, 1.6 Hz,2H), 7.02 (td, J = 7.9, 1.5 Hz, 2H), 6.95 – 6.88 (m, 2H), 5.35 (t, J = 7.2 Hz,1H), 2.21 – 2.11 (m, 1H), 2.07 – 1.96 (m, 2H), 1.87 – 1.76 (m, 1H), 0.86 (t, J = 7.6 Hz, 3H), 0.81 (t, J = 7.5 Hz, 3H); 13 C NMR (126 MHz, CDCl3)δ 146.3 (d, J =35.3 Hz), 141.6, 140.6 (d, J = 1.7 Hz), 138.5 (d, J = 13.3 Hz), 138.3 (d, J = 12.1Hz), 137.7 (d, J = 13.3 Hz), 136.3 (d, J = 6.9 Hz), 134.9 (d, J = 2.3 Hz), 134.0(d, J = 20.8 Hz), 133.4 (d, J = 2.3 Hz), 133.0, 132.9, 132.8, 131.9, 131.5 (d, J =6.4 Hz), 128.5, 128.4, 128.3, 128.1, 128.0, 127.9, 127.6, 127.4 (d, J = 10.4Hz), 127.3, 126.9, 124.9 (d, J= 41.6 Hz), 24.2, 21.2, 14.2, 13.5; 31 P NMR (202MHz, CDCl3)δ -15.48.

[0085] Example 26 Synthesis of (R,E)-(2-(2-(oct-4-en-4-yl)naphthalen-1-yl)phenyl)diphenylphosphine

[0086] In a 25.0 mL dry Schlenk tube with a stir bar, (1,5-cyclooctadiene)iridium(I) chloride dimer (3.4 mg, 0.01 mmol, 0.05 equiv) and (R)- N 2-Dimethyl-[(S)-1,1'-spirodihydroindane-7,7'-diyl]phosphoramidite (7.3 mg, 0.022 mmol, 0.11 equivalents). The resulting mixed solution was stirred at room temperature for 1 hour. Then, (2-(naphthalen-1-yl)phenyl)diphenylphosphine (77.6 mg, 0.2 mmol) and 4-octyne (110.2 mg, 1.0 mmol) were added under argon. The resulting mixture was stirred at 70°C for 72 hours. After cooling to room temperature, the solvent was evaporated under reduced pressure. The product was separated by chromatography on a 300-400 mesh silica gel column with petroleum ether:dichloromethane (10:1) as the eluent and dried under vacuum to obtain the product in a 53% yield with an enantiomeric excess of 85%. 1 H NMR (500 MHz, CDCl3)δ 8.82 (s, 1H), 8.09 (d,J = 8.3 Hz, 1H), 7.54 (m, 1H), 7.48 – 7.42 (m, 1H), 7.40 (m, 2H), 7.29 (m,4H), 7.21 – 7.16 (m, 1H), 7.16 – 7.06 (m, 5H), 7.01 – 6.94 (m, 3H), 5.50 (qd,J = 6.7, 1.5 Hz, 1H); 13 C NMR (126 MHz, CDCl3)δ 151.2, 146.6, 144.2 (d, J = 6.5Hz), 143.6 (d, J = 34.7 Hz), 137.5 (d, J = 12.7 Hz), 137.3 (d, J = 13.9 Hz), 137.2(d, J = 11.0 Hz), 137.1, 135.2 (d, J= 2.9 Hz), 133.7 (d, J = 20.8 Hz), 133.3,132.8 (d, J = 18.5 Hz), 130.8 (d, J = 6.4 Hz), 128.9, 128.6, 128.4, 128.4 (d, J =2.3 Hz), 128.2, 128.2, 128.13, 128.08, 127.9, 127.7 (d, J = 1.7 Hz), 126.5,125.9, 17.4 (d, J = 1.7 Hz), 14.0; 31 P NMR (202 MHz, CDCl3)δ -15.48.

[0087] Example 27 Synthesis of (R,E)-(2-(2-(2,9-dimethyldec-5-en-5-yl)naphthalen-1-yl)phenyl)diphenylphosphine

[0088] In a 25.0 mL dry Schlenk tube with a stir bar, (1,5-cyclooctadiene)iridium(I) chloride dimer (3.4 mg, 0.01 mmol, 0.05 equiv) and (R)- N 1,1'-Dimethyl-[(S)-1,1'-spirodihydroindane-7,7'-diyl]phosphoramidite (7.3 mg, 0.022 mmol, 0.11 equivalents). The resulting mixed solution was stirred at room temperature for 1 hour. Then, (2-(naphthalen-1-yl)phenyl)diphenylphosphine (77.6 mg, 0.2 mmol) and 2,9-dimethyldec-5-yne (166.3 mg, 1.0 mmol) were added under argon. The resulting mixture was stirred at 70°C for 72 hours. After cooling to room temperature, the solvent was evaporated under reduced pressure. The product was separated by chromatography on a 300-400 mesh silica gel column with petroleum ether:dichloromethane (10:1) as the eluent and dried under vacuum to obtain the product in a 33% yield with an enantiomeric excess of 93%. 1 H NMR (500 MHz, CDCl3)δ 7.85 (d, J =8.4 Hz, 1H), 7.82 (d, J = 8.1 Hz, 1H), 7.46 – 7.41 (m, 2H), 7.41 – 7.37 (m,2H), 7.35 – 7.32 (m, 1H), 7.31 (d, J= 7.6 Hz, 1H), 7.28 (d, J = 3.4 Hz, 3H),7.21 – 7.15 (m, 3H), 7.11 (t, J = 7.5 Hz, 2H), 7.01 – 6.94 (m, 3H), 6.88 (d, J =8.4 Hz, 1H), 5.34 (t, J = 7.2 Hz, 1H), 2.21 – 2.10 (m, 1H), 2.05 – 1.96 (m,1H), 1.97 – 1.88 (m, 1H), 1.77 – 1.68 (m, 1H), 1.46 – 1.38 (m, 2H), 1.16 (q, J = 7.2 Hz, 2H), 1.08 – 1.01 (m, 2H), 0.85 (t, J = 5.9 Hz, 6H), 0.80 (dd, J = 6.7,2.0 Hz, 6H); 13 C NMR (126 MHz, CDCl3)δ 146.3 (d, J = 35.3 Hz), 141.0, 140.7,138.6 (d, J = 13.9 Hz), 138.3 (d, J = 12.1 Hz), 137.9 (d, J = 13.9 Hz), 136.1 (d, J =6.4 Hz), 135.0 (d, J = 2.9 Hz), 134.0 (d, J = 21.4 Hz), 133.0 (d, J = 2.2 Hz),132.8 (d, J = 17.3 Hz), 132.5 (d, J = 2.9 Hz), 131.9, 131.5 (d, J = 6.4 Hz), 128.4(d, J = 13.9 Hz), 128.2, 128.03, 127.98, 127.9, 127.6, 127.4 (d, J = 6.9 Hz),127.3, 126.9, 124.9 (d, J= 48.6 Hz), 38.8, 37.9, 29.2, 28.1, 27.6, 26.0, 22.7,22.6, 22.5, 22.3; 31 P NMR (202 MHz, CDCl3)δ -15.45.

[0089] Example 28 Synthesis of (R,E)-diphenyl(2-(2-(1-phenylpropyl-1-en-2-yl)naphthalen-1-yl)phenyl)phosphine

[0090] In a 25.0 mL dry Schlenk tube with a stir bar, (1,5-cyclooctadiene)iridium(I) chloride dimer (3.4 mg, 0.01 mmol, 0.05 equiv) and (R)- N 1,1'-Dimethyl-[(S)-1,1'-spirodihydroindane-7,7'-diyl]phosphoramidite (7.3 mg, 0.022 mmol, 0.11 equivalents). The resulting mixed solution was stirred at room temperature for 1 hour. Then, (2-(naphthalen-1-yl)phenyl)diphenylphosphine (77.6 mg, 0.2 mmol) and prop-1-yn-1-ylbenzene (116.2 mg, 1.0 mmol) were added under argon. The resulting mixture was stirred at 90°C for 72 hours. After cooling to room temperature, the solvent was evaporated under reduced pressure. The product was separated by chromatography on a 300-400 mesh silica gel column with petroleum ether:dichloromethane (10:1) as the eluent and dried under vacuum to obtain the product in a 32% yield with an enantiomeric excess of 89%. 1 H NMR (500 MHz, CDCl3)δ 7.89 (d, J = 8.6Hz, 1H), 7.80 (d, J = 8.4 Hz, 1H), 7.52 (d, J = 8.4 Hz, 1H), 7.46 – 7.42 (m, 1H), 7.41 – 7.38 (m, 1H), 7.38 – 7.33 (m, 2H), 7.33 – 7.29 (m, 1H), 7.29 – 7.21(m, 3H), 7.20 – 7.15 (m, 2H), 7.14 – 7.07 (m, 3H), 7.06 – 7.02 (m, 4H), 7.02– 7.00 (m, 2H), 6.98 (d, J = 1.3 Hz, 1H), 6.98 – 6.95 (m, 2H), 6.44 (s, 1H), 1.90 (d, J= 1.3 Hz, 3H); 13 C NMR (101 MHz, CDCl3)δ 146.0 (d, J = 34.5 Hz), 142.0,138.5, 138.3 (d, J = 12.3 Hz), 138.1, 138.0 (d, J = 13.1 Hz), 137.4 (d, J = 13.2Hz), 136.3, 135.0 (d, J = 2.3 Hz), 134.0 (d, J = 21.3 Hz), 132.9 (d, J = 18.2 Hz),132.1, 132.0 (d, J = 6.4 Hz), 131.7 (d, J = 2.7 Hz), 128.9, 128.4, 128.3, 128.1(d, J = 1.3 Hz), 128.0 (d, J = 3.2 Hz), 127.9, 127.8, 127.6, 127.5 (d, J = 3.6 Hz),127.1, 126.4 (d, J = 48.6 Hz), 125.2 (d, J = 31.3 Hz), 20.0 (d, J = 2.3 Hz); 31 P NMR(162 MHz, CDCl3)δ -15.29.

[0091] Example 29 Synthesis of Ethyl (R)-3-(1-(2-(diphenylphosphino)phenyl)naphthalen-2-yl)propionate

[0092] In a 25 mL dry Schlenk tube with a stir bar, (1,5-cyclooctadienyl)iridium(I) chloride dimer (3.4 mg, 0.01 mmol, 0.05 equiv) and (R)-(-)-(3,5-dioxo-4-phosphino-cycloheptyl[2,1-A,3,4-A']dinaphthyl)dimethylamine (8.0 mg, 0.022 mmol, 0.11 equiv) were added to 2.0 mL of toluene under Ar. The resulting mixed solution was stirred at room temperature for 1 h. Then, (2-(naphthalen-1-yl)phenyl)diphenylphosphine (77.6 mg, 0.2 mmol) and ethyl acrylate (100.0 mg, 1.0 mmol) were added under argon. The resulting mixture was stirred at 150°C for 48 hours. After cooling to room temperature, the solvent was evaporated under reduced pressure. The product was separated by 300-400 mesh silica gel chromatography column with petroleum ether:ethyl acetate = 20:1 as the eluent and dried in vacuo to obtain the product with a yield of 77% and an enantiomeric excess of 91%. 1 H NMR (400 MHz, CDCl3)δ 7.78 (d, J =8.5 Hz, 1H), 7.74 (d, J = 7.4 Hz, 1H), 7.43 (td, J = 7.1, 2.1 Hz, 1H), 7.39 –7.31 (m, 3H), 7.30 – 7.21 (m, 5H), 7.21 – 7.16 (m, 2H), 7.12 – 7.05 (m, 4H),7.04 – 6.95 (m, 3H), 4.02 (q, J = 7.2 Hz, 2H), 2.67 – 2.50 (m, 2H), 2.49 – 2.28(m, 2H), 1.15 (t, J = 7.2 Hz, 3H); 13 C NMR (101 MHz, CDCl3)δ 172.7, 145.0 (d, J =33.2 Hz), 138.3 (d, J = 12.3 Hz), 137.3 (d, J = 6.8 Hz), 136.8 (d, J = 12.3 Hz),136.0, 134.2, 133.7 (d, J = 3.2 Hz), 133.5 (d, J = 4.1 Hz), 132.9, 131.7, 130.7(d,J = 5.9 Hz), 129.0, 128.3, 128.2, 128.0 (d, J = 3.2 Hz), 127.9, 127.6 (d, J =27.7 Hz), 126.4, 125.5, 124.8, 60.1, 35.0, 28.8, 14.1; 31 P NMR (162 MHz, CDCl3)δ -15.39.

[0093] Example 30 Synthesis of Ethyl (R)-3-(1-(2-(diphenylphosphino)-5-methylphenyl)naphthalen-2-yl)propionate

[0094] In a 25 mL dry Schlenk tube with a stir bar, (1,5-cyclooctadienyl)iridium(I) chloride dimer (3.4 mg, 0.01 mmol, 0.05 equiv) and (R)-(-)-(3,5-dioxo-4-phosphino-cycloheptyl[2,1-A,3,4-A']dinaphthyl)dimethylamine (8.0 mg, 0.022 mmol, 0.11 equiv) were added to 2.0 mL of toluene under Ar. The resulting mixed solution was stirred at room temperature for 1 h. Then, (5-methyl-2-(naphthalen-1-yl)phenyl)diphenylphosphine (80.4 mg, 0.2 mmol) and ethyl acrylate (100.0 mg, 1.0 mmol) were added under argon, and the resulting mixture was stirred at 150°C for 48 hours. After cooling to room temperature, the solvent was evaporated under reduced pressure, and the product was separated by 300-400 mesh silica gel chromatography column with petroleum ether:ethyl acetate = 20:1 as the eluent. The product was dried in vacuo to obtain the product with a yield of 64% and an enantiomeric excess of 90%. 1 H NMR (500 MHz, CDCl3)δ 7.80(d, J = 8.4 Hz, 1H), 7.76 (dd, J = 8.2, 1.7 Hz, 1H), 7.35 (d, J = 8.5 Hz, 1H), 7.33– 7.04 (m, 13H), 7.03 – 6.98 (m, 3H), 4.09 (qd, J = 7.2, 1.1 Hz, 2H), 2.68 –2.54 (m, 2H), 2.49 – 2.41 (m, 1H), 2.38 (s, 3H), 2.35 – 2.28 (m, 1H), 1.19(t, J = 7.2 Hz, 3H);13 C NMR (126 MHz, CDCl3)δ 173.1, 145.3 (d, J = 34.1 Hz),139.3, 137.7 (d, J = 7.5 Hz), 137.6 – 137.3 (m), 136.0 (d, J = 2.3 Hz), 134.7 (d, J = 10.4 Hz), 134.5 (d, J = 2.3 Hz), 133.7, 133.5 (d, J = 2.3 Hz), 133.1 (d, J = 2.3Hz), 131.9, 131.6 (d, J = 6.4 Hz), 128.9, 128.3 – 128.1 (m), 127.6, 126.6 (d, J =24.3 Hz), 125.3 (d, J = 77.4 Hz), 60.3, 35.1, 28.9 (d, J = 2.3 Hz), 21.4, 14.2; 31 PNMR (202 MHz, CDCl3)δ -16.60.

[0095] Example 31 Synthesis of Ethyl (R)-3-(1-(2-(diphenylphosphino)-4-methylphenyl)naphthalen-2-yl)propionate

[0096] In a 25 mL dry Schlenk tube with a stir bar, (1,5-cyclooctadienyl)iridium(I) chloride dimer (3.4 mg, 0.01 mmol, 0.05 equiv) and (R)-(-)-(3,5-dioxo-4-phospho-cycloheptyl[2,1-A,3,4-A']dinaphthyl)dimethylamine (8.0 mg, 0.022 mmol, 0.11 equiv) were added to 2.0 mL of tetrahydrofuran under Ar. The resulting mixed solution was stirred at room temperature for 1 h. Then, (4-methyl-2-(naphthalen-1-yl)phenyl)diphenylphosphine (80.4 mg, 0.2 mmol) and ethyl acrylate (100.0 mg, 1.0 mmol) were added under argon. The resulting mixture was stirred at 150°C for 48 hours. After cooling to room temperature, the solvent was evaporated under reduced pressure. The product was separated by 300-400 mesh silica gel chromatography column with petroleum ether:ethyl acetate = 20:1 as the eluent and dried in vacuo to obtain the product with a yield of 80% and an enantiomeric excess of 99%.1 H NMR (500 MHz, CDCl3)δ7.70 (d, J = 8.5 Hz, 1H), 7.66 (d, J = 7.2 Hz, 1H), 7.25 (d, J = 8.5 Hz, 1H), 7.22– 7.19 (m, 1H), 7.19 – 7.15 (m, 4H), 7.11 – 7.07 (m, 2H), 7.05 (dd, J = 6.9,2.6 Hz, 2H), 7.04 – 6.99 (m, 3H), 6.99 – 6.96 (m, 1H), 6.94 – 6.90 (m, 3H),3.95 (q, J = 7.1 Hz, 2H), 2.58 – 2.50 (m, 1H), 2.50 – 2.43 (m, 1H), 2.39 – 2.31(m, 1H), 2.28 – 2.20 (m, 4H), 1.08 (t, J = 7.2 Hz, 3H); 13 C NMR (126 MHz, CDCl3)δ173.0, 142.2 (d, J = 33.5 Hz), 137.9 (d, J = 12.1 Hz), 137.5 (d, J = 7.5 Hz),137.4, 137.2 (d, J = 3.5 Hz), 137.1 (d, J = 2.9 Hz), 136.3 (d, J = 2.3 Hz), 134.8(d, J = 2.3 Hz), 133.8 (d, J = 1.6 Hz), 133.7 (d, J = 2.9 Hz), 133.3 (d, J = 2.9 Hz),131.9, 130.8 (d, J = 6.4 Hz), 130.2, 128.24, 128.19, 128.1, 127.98 (d, J = 6.4Hz), 127.93, 127.5, 126.5 (d, J= 14.5 Hz), 125.4, 124.8, 60.1, 35.1, 28.8 (d, J = 2.3 Hz), 21.4, 14.2; 31 P NMR (202 MHz, CDCl3)δ -15.22.

[0097] Example 32 Synthesis of Ethyl (R)-3-(1-(2-(diphenylphosphino)phenyl)-4-methylnaphthalen-2-yl)propionate

[0098] In a 25 mL dry Schlenk tube with a stir bar, (1,5-cyclooctadienyl)iridium(I) chloride dimer (3.4 mg, 0.01 mmol, 0.05 equiv) and (R)-(-)-(3,5-dioxo-4-phosphino-cycloheptyl[2,1-A,3,4-A']dinaphthyl)dimethylamine (8.0 mg, 0.022 mmol, 0.11 equiv) were added to 2.0 mL of toluene under Ar. The resulting mixed solution was stirred at room temperature for 1 h. Then, (2-(4-methylnaphthalen-1-yl)phenyl)diphenylphosphine (80.4 mg, 0.2 mmol) and ethyl acrylate (100.0 mg, 1.0 mmol) were added under argon. The resulting mixture was stirred at 150°C for 48 hours. After cooling to room temperature, the solvent was evaporated under reduced pressure. The product was separated by 300-400 mesh silica gel chromatography column with petroleum ether:ethyl acetate = 20:1 as the eluent and dried in vacuo to obtain the product with a yield of 66% and an enantiomeric excess of 93%. 1 H NMR (400 MHz, CDCl3)δ 7.9(d, J = 8.4 Hz, 1H), 7.45 (t, J = 7.3 Hz, 1H), 7.40 (d, J = 7.5 Hz, 1H), 7.38 –7.32 (m, 2H), 7.29 – 7.25 (m, 3H), 7.25 – 7.22 (m, 1H), 7.21 – 7.16 (m, 3H), 7.16 – 7.06 (m, 4H), 7.04 – 6.96 (m, 3H), 4.04 (q, J = 7.2 Hz, 2H), 2.71 (s,3H), 2.58 – 2.48 (m, 2H), 2.48 – 2.39 (m, 1H), 2.37 – 2.27 (m, 1H), 1.18 (t, J = 7.2 Hz, 3H).; 13C NMR (126 MHz, CDCl3) δ 173.0, 145.4 (d, J = 33.5 Hz), 138.4(d, J = 11.6 Hz), 137.1 (d, J = 12.1 Hz), 137.0 (d, J = 12.6 Hz), 135.8 (d, J = 7.2Hz), 135.6 (d, J = 1.7 Hz), 134.4 (d, J = 2.3 Hz), 134.2, 133.7 (d, J = 5.8 Hz),133.6 (d, J = 6.4 Hz), 133.1 (d, J = 2.3 Hz), 131.1 (d, J = 6.0 Hz), 129.1, 128.3(d, J = 2.9 Hz), 128.22 (d, J = 6.4 Hz), 1128.20, 128.0 (d, J = 6.9 Hz), 127.2 (d, J = 31.2 Hz), 125.2, 124.8, 123.8, 60.2, 35.2, 28.8, 19.6, 14.2; 31 P NMR (162MHz, CDCl3)δ -15.72.

[0099] Example 33 Synthesis of Ethyl (R)-3-(1-(2-(diphenylphosphino)-4,5-dimethylphenyl)naphthalen-2-yl)propionate

[0100] In a 25 mL dry Schlenk tube with a stir bar, (1,5-cyclooctadienyl)iridium(I) chloride dimer (3.4 mg, 0.01 mmol, 0.05 equiv) and (R)-(-)-(3,5-dioxo-4-phosphino-cycloheptyl[2,1-A,3,4-A']dinaphthyl)dimethylamine (8.0 mg, 0.022 mmol, 0.11 equiv) were added to 2.0 mL of toluene under Ar. The resulting mixed solution was stirred at room temperature for 1 h. Then, (4,5-dimethyl-2-(naphthalen-1-yl)phenyl)diphenylphosphine (83.2 mg, 0.2 mmol) and ethyl acrylate (100.0 mg, 1.0 mmol) were added under argon, and the resulting mixture was stirred at 150°C for 48 hours. After cooling to room temperature, the solvent was evaporated under reduced pressure, and the product was separated by 300-400 mesh silica gel chromatography column with petroleum ether:ethyl acetate = 20:1 as the eluent. The product was dried in vacuo to obtain the product with a yield of 56% and an enantiomeric excess of 88%. 1 H NMR (500 MHz, CDCl3)δ7.80 (dd, J = 13.3, 8.3 Hz, 2H), 7.37 – 7.31 (m, 2H), 7.30 – 7.27 (m, 3H), 7.22– 7.17 (m, 3H), 7.17 – 7.13 (m, 2H), 7.13 – 7.09 (m, 2H), 7.08 – 7.00 (m,4H), 4.11 – 4.03 (m, 2H), 2.71 – 2.56 (m, 2H), 2.51 – 2.43 (m, 1H), 2.37 –2.32 (m, 1H), 2.30 (s, 2H), 2.28 (s, 1H), 1.21 (td, J = 7.2, 2.0 Hz, 3H); 13 C NMR (126 MHz, CDCl3) δ 173.1, 142.8 (d, J = 34.1 Hz), 137.8 (d, J = 48.6 Hz), 137.7(d, J = 5.2 Hz), 137.5 (d, J = 12.1 Hz), 136.14, 136.07 (d, J = 1.6 Hz), 135.4 (d, J = 2.9 Hz), 134.6 (d, J= 10.4 Hz), 133.6, 133.4, 133.2 (d, J = 2.3 Hz), 131.9 (d, J = 6.9 Hz), 131.8, 128.2 (d, J = 6.4 Hz), 128.1 (d, J = 4.0 Hz), 128.0 (d, J = 6.4Hz), 127.7 (d, J = 37.6 Hz), 126.6 (d, J = 40.5 Hz), 125.4, 124.8, 60.2, 35.1,28.8, 19.7 (d, J = 4.0 Hz), 14.2; 31 P NMR (202 MHz, CDCl3)δ -16.52.

[0101] Example 34 Synthesis of Ethyl (R)-3-(1-(2-(diphenylphosphino)phenyl)-4-phenylnaphthalen-2-yl)propionate

[0102] In a 25 mL dry Schlenk tube with a stir bar, (1,5-cyclooctadienyl)iridium(I) chloride dimer (3.4 mg, 0.01 mmol, 0.05 equiv) and (R)-(-)-(3,5-dioxo-4-phosphino-cycloheptyl[2,1-A,3,4-A']dinaphthyl)dimethylamine (8.0 mg, 0.022 mmol, 0.11 equiv) were added to 2.0 mL of toluene under Ar. The resulting mixed solution was stirred at room temperature for 1 h. Diphenyl(2-(4-phenylnaphthalen-1-yl)phenyl)phosphine (92.8 mg, 0.2 mmol) and ethyl acrylate (100.0 mg, 1.0 mmol) were then added under argon. The resulting mixture was stirred at 150°C for 48 hours. After cooling to room temperature, the solvent was evaporated under reduced pressure. The product was separated by chromatography on a 300-400 mesh silica gel column with petroleum ether:ethyl acetate = 20:1 as the eluent and dried in vacuo to obtain the product in a yield of 55% and an enantiomeric excess of 93%. 1 H NMR (500 MHz, CDCl3)δ 7.85(d, J= 8.4 Hz, 1H), 7.57 – 7.53 (m, 2H), 7.52 – 7.47 (m, 3H), 7.46 – 7.40 (m,2H), 7.37 – 7.33 (m, 1H), 7.31 – 7.26 (m, 6H), 7.24 – 7.19 (m, 2H), 7.19 –7.09 (m, 4H), 7.08 – 7.02 (m, 3H), 4.03 (q, J = 7.2 Hz, 2H), 2.68 – 2.60 (m,1H), 2.60 – 2.52 (m, 1H), 2.50 – 2.42 (m, 1H), 2.39 – 2.31 (m, 1H), 1.17 (t, J = 7.2 Hz, 3H); 13 C NMR (126 MHz, CDCl3)δ 172.9, 145.0 (d, J = 32.9 Hz), 140.5 (d, J = 72.8 Hz), 138.4 (d, J = 12.1 Hz), 137.0, 136.91, 136.8 (d, J = 4.7 Hz), 136.7,135.6 (d, J = 1.6 Hz), 134.3, 133.8 (d, J = 12.7 Hz), 133.7 (d, J = 13.3 Hz), 133.3(d, J = 2.1 Hz), 131.0 (d, J = 5.8 Hz), 130.2, 130.0, 129.1, 128.4 (d, J = 4.0 Hz),128.3 (d, J = 5.8 Hz), 128.2, 128.1 (d, J = 6.9 Hz), 127.9, 127.6, 127.2, 126.9,125.7, 125.4, 125.0, 60.2, 35.1, 28.9 (d, J = 2.9 Hz), 14.2; 31 P NMR (202 MHz,CDCl3)δ -15.10.

[0103] Example 35 Synthesis of Ethyl (R)-3-(1-(2-(diphenylphosphino)-5-methoxyphenyl)naphthalen-2-yl)propionate

[0104] In a 25 mL dry Schlenk tube with a stir bar, (1,5-cyclooctadienyl)iridium(I) chloride dimer (3.4 mg, 0.01 mmol, 0.05 equiv) and (R)-(-)-(3,5-dioxo-4-phosphino-cycloheptyl[2,1-A,3,4-A']dinaphthyl)dimethylamine (8.0 mg, 0.022 mmol, 0.11 equiv) were added to 2.0 mL of toluene under Ar. The resulting mixed solution was stirred at room temperature for 1 h. Then, (4-methoxy-2-(naphthalen-1-yl)phenyl)diphenylphosphine (83.6 mg, 0.2 mmol) and ethyl acrylate (100.0 mg, 1.0 mmol) were added under argon. The resulting mixture was stirred at 150°C for 48 hours. After cooling to room temperature, the solvent was evaporated under reduced pressure. The product was separated by 300-400 mesh silica gel chromatography column with petroleum ether:ethyl acetate = 20:1 as the eluent and dried in vacuo to obtain the product with a yield of 68% and an enantiomeric excess of 82%. 1 H NMR (500 MHz, CDCl3)δ 7.86(d, J = 8.4 Hz, 1H), 7.82 (d, J = 8.1 Hz, 1H), 7.40 (d, J = 8.5 Hz, 1H), 7.38 –7.34 (m, 1H), 7.33 – 7.28 (m, 4H), 7.25 – 7.19 (m, 3H), 7.19 – 7.14 (m, 3H),7.12 – 7.09 (m, 1H), 7.08 – 7.04 (m, 2H), 7.00 (dd, J = 8.5, 2.7 Hz, 1H), 6.85(dd, J = 3.7, 2.7 Hz, 1H), 4.09 (qd, J = 7.1, 1.1 Hz, 2H), 3.83 (s, 3H), 2.76 –2.60 (m, 2H), 2.56 – 2.47 (m, 1H), 2.43 – 2.34 (m, 1H), 1.23 (t, J = 7.2 Hz,3H); 13 C NMR (126 MHz, CDCl3) δ 172.9, 160.3, 146.9 (d,J = 36.4 Hz), 137.8 (d, J =12.1 Hz), 137.6 (d, J = 12.7 Hz), 137.4 (d, J = 6.9 Hz), 136.0 (d, J = 2.9 Hz),135.8 (d, J = 2.3 Hz), 133.5, 133.3 (d, J = 2.9 Hz), 132.9 (d, J = 2.3 Hz), 131.7,128.9 (d, J = 9.2 Hz), 128.2 (d, J = 6.4 Hz), 128.1 (d, J = 2.3 Hz), 128.03 (d, J =3.5 Hz), 127.96, 127.6, 126.5 (d, J = 21.4 Hz), 126.0, 125.0, 115.8 (d, J = 6.9Hz), 114.2, 60.2, 55.2, 35.1, 28.7, 14.1; 31 P NMR (202 MHz, CDCl3)δ -17.63.

[0105] Example 36 Synthesis of Ethyl (R)-3-(1-(2-(diphenylphosphino)phenyl)-4-methoxynaphthalen-2-yl)propionate

[0106] In a 25 mL dry Schlenk tube with a stir bar, (1,5-cyclooctadienyl)iridium(I) chloride dimer (3.4 mg, 0.01 mmol, 0.05 equiv) and (R)-(-)-(3,5-dioxo-4-phosphino-cycloheptyl[2,1-A,3,4-A']dinaphthyl)dimethylamine (8.0 mg, 0.022 mmol, 0.11 equiv) were added to 2.0 mL of toluene under Ar. The resulting mixed solution was stirred at room temperature for 1 h. Then, (2-(4-methoxynaphthalen-1-yl)phenyl)diphenylphosphine (83.6 mg, 0.2 mmol) and ethyl acrylate (100.0 mg, 1.0 mmol) were added under argon. The resulting mixture was stirred at 150°C for 48 hours. After cooling to room temperature, the solvent was evaporated under reduced pressure. The product was separated by 300-400 mesh silica gel chromatography column with petroleum ether:ethyl acetate = 20:1 as the eluent and dried in vacuo to obtain the product with a yield of 21% and an enantiomeric excess of 90%. 1 H NMR (500 MHz, CDCl3)δ 8.19(d, J = 8.4 Hz, 1H), 7.45 (td, J = 7.4, 1.5 Hz, 1H), 7.39 (td, J = 7.6, 1.5 Hz,1H), 7.34 – 7.30 (m, 2H), 7.30 – 7.26 (m, 4H), 7.23 (ddd, J = 7.5, 4.4, 1.7 Hz,1H), 7.21 – 7.14 (m, 3H), 7.14 – 7.09 (m, 2H), 7.09 – 7.05 (m, 1H), 7.00 (tt, J = 7.3, 1.4 Hz, 2H), 6.89 (d, J = 8.4 Hz, 1H), 6.69 (s, 1H), 4.05 (q, J = 7.2 Hz,2H), 4.02 (s, 3H), 2.65 – 2.52 (m, 2H), 2.48 – 2.41 (m, 1H), 2.40 – 2.32 (m,1H), 1.19 (t, J = 7.1 Hz, 3H); 13 C NMR (126 MHz, CDCl3)δ 173.0, 155.2, 145.3 (d, J= 33.5 Hz), 138.9 (d, J = 11.0 Hz), 137.2 (d, J = 12.7 Hz), 137.0 (d, J = 12.7 Hz),136.3 (d, J = 1.7 Hz), 134.3 (d, J = 2.3 Hz), 134.0 (d, J = 2.3 Hz), 133.8 (d, J =12.7 Hz), 133.6 (d, J = 11.6 Hz), 131.5 (d, J = 5.8 Hz), 129.9 (d, J = 7.5 Hz),129.1, 128.33, 128.27, 128.1 (d, J = 6.9 Hz), 127.7, 126.2 (d, J = 21.4 Hz),124.3, 124.1, 121.5, 104.4, 60.8, 55.5, 35.3, 29.4 (d, J = 2.9 Hz), 14.2; 31 P NMR(202 MHz, CDCl3)δ -15.48.

[0107] Example 37 Synthesis of Ethyl (R)-3-(1-(6-(diphenylphosphino)benzo[d][1,3]dioxol-5-yl)naphthalen-2-yl)propanoate

[0108] In a 25 mL dry Schlenk tube with a stir bar, (1,5-cyclooctadienyl)iridium(I) chloride dimer (3.4 mg, 0.01 mmol, 0.05 equiv) and (R)-(-)-(3,5-dioxo-4-phosphino-cycloheptyl[2,1-A,3,4-A']dinaphthyl)dimethylamine (8.0 mg, 0.022 mmol, 0.11 equiv) were added to 2.0 mL of toluene under Ar. The resulting mixed solution was stirred at room temperature for 1 h. Then, (6-(naphthalen-1-yl)benzo[d][1,3]dihydroxy-5-yl)diphenylphosphine (86.2 mg, 0.2 mmol) and ethyl acrylate (100.0 mg, 1.0 mmol) were added under argon. The resulting mixture was stirred at 150°C for 48 hours. After cooling to room temperature, the solvent was evaporated under reduced pressure. The product was separated by 300-400 mesh silica gel chromatography column with petroleum ether:ethyl acetate = 20:1 as the eluent and dried in vacuo to obtain the product with a yield of 56% and an enantiomeric excess of 88%. 1 H NMR (500 MHz,CDCl3)δ 1 H NMR (500 MHz, Chloroform- d ) δ 7.79 (dd, J = 15.8, 8.2 Hz, 2H), 7.37 –7.30 (m, 2H), 7.30 – 7.25 (m, 3H), 7.22 – 7.16 (m, 3H), 7.16 – 7.08 (m, 4H),7.03 – 6.97 (m, 2H), 6.80 (d, J = 2.4 Hz, 1H), 6.72 (d, J = 3.5 Hz, 1H), 6.02(dd, J = 10.1, 1.5 Hz, 2H), 4.06 (q, J = 7.1 Hz, 2H), 2.75 – 2.66 (m, 1H), 2.64 –2.55 (m, 1H), 2.54 – 2.42 (m, 1H), 2.39 – 2.25 (m, 1H), 1.20 (t, J = 7.2 Hz,3H); 13 C NMR (126 MHz, CDCl3)δ 172.9, 148.8, 147.5, 139.9 (d, J = 37.0 Hz), 137.7(d, J= 12.7 Hz), 137.4 (d, J = 12.7 Hz), 137.2 (d, J = 8.1 Hz), 136.4, 133.5 (d, J =19.7 Hz), 133.3 (d, J = 2.3 Hz), 131.9, 130.7 (d, J = 12.1 Hz), 128.4 (d, J = 6.4Hz), 128.3 (d, J = 2.9 Hz), 128.2 (d, J = 7.5 Hz), 127.7, 126.5 (d, J = 15.6 Hz),125.7, 125.1, 113.7, 111.1 (d, J = 6.9 Hz), 101.4, 60.3, 35.1, 28.8 (d, J = 2.9Hz), 14.3; 31 P NMR (202 MHz, CDCl3)δ -15.49.

[0109] Example 38 Synthesis of Ethyl (R)-3-(1-(2-(diphenylphosphino)-4-fluorophenyl)naphthalen-2-yl)propionate

[0110] In a 25 mL dry Schlenk tube with a stir bar, (1,5-cyclooctadienyl)iridium(I) chloride dimer (3.4 mg, 0.01 mmol, 0.05 equiv) and (R)-(-)-(3,5-dioxo-4-phospho-cycloheptyl[2,1-A,3,4-A']dinaphthyl)dimethylamine (8.0 mg, 0.022 mmol, 0.11 equiv) were added to 2.0 mL of o-xylene under Ar. The resulting mixed solution was stirred at room temperature for 1 h. Then, (5-fluoro-2-(naphthalen-1-yl)phenyl)diphenylphosphine (81.2 mg, 0.2 mmol) and ethyl acrylate (100.0 mg, 1.0 mmol) were added under argon. The resulting mixture was stirred at 150°C for 48 hours. After cooling to room temperature, the solvent was evaporated under reduced pressure. The product was separated by 300-400 mesh silica gel chromatography column with petroleum ether:ethyl acetate = 20:1 as the eluent and dried in vacuo to obtain the product with a yield of 77% and an enantiomeric excess of 92%. 1 H NMR (500 MHz, CDCl3)δ 7.81 (d,J = 8.4 Hz, 1H), 7.75 (dd, J = 8.1, 1.4 Hz, 1H), 7.34 (d, J = 8.5 Hz, 1H),7.32 – 7.26 (m, 4H), 7.21 – 7.15 (m, 5H), 7.13 – 7.06 (m, 3H), 7.03 – 7.00(m, 1H), 7.00 – 6.96 (m, 2H), 6.93 (d, J = 8.1 Hz, 1H), 4.05 (q, J = 7.2 Hz, 2H),2.63 – 2.55 (m, 1H), 2.55 – 2.48 (m, 1H), 2.47 – 2.40 (m, 1H), 2.38 – 2.30(m, 1H), 1.19 (t, J = 7.1 Hz, 3H); 13 C NMR (126 MHz, CDCl3) δ 172.9, 163.3,161.3, 141.7 (dd, J = 15.9, 4.3 Hz), 140.6 (dd, J = 31.8, 3.5 Hz), 136.5 (d, J =1.7 Hz), 136.2 (d, J = 6.9 Hz), 136.1 (d, J = 12.1 Hz), 135.9 (d, J = 12.1 Hz),133.8 (d, J = 20.8 Hz), 133.1 (d, J = 2.3 Hz), 132.5 (dd, J = 7.5, 5.2 Hz), 131.9,128.7 (d, J = 11.0 Hz), 128.6 (d, J = 6.4 Hz), 128.4, 128.3 (d, J = 6.9 Hz), 127.1(d, J = 149.1 Hz), 126.3, 125.4 (d, J = 89.6 Hz), 120.5 (d, J= 21.4 Hz), 116.3 (d, J = 21.4 Hz), 60.3, 35.1 (d, J = 1.7 Hz), 28.9 (d, J = 2.9 Hz), 14.3; 31 P NMR (202MHz, CDCl3)δ -14.68.

[0111] Example 39 Synthesis of Ethyl (R)-3-(1-(2-(diphenylphosphino)-4,5-difluorophenyl)naphthalen-2-yl)propionate

[0112] In a 25 mL dry Schlenk tube with a stir bar, (1,5-cyclooctadienyl)iridium(I) chloride dimer (3.4 mg, 0.01 mmol, 0.05 equiv) and (R)-(-)-(3,5-dioxo-4-phosphino-cycloheptyl[2,1-A,3,4-A']dinaphthyl)dimethylamine (8.0 mg, 0.022 mmol, 0.11 equiv) were added to 2.0 mL of toluene under Ar. The resulting mixed solution was stirred at room temperature for 1 h. Then, (4,5-difluoro-2-(naphthalen-1-yl)phenyl)diphenylphosphine (84.8 mg, 0.2 mmol) and ethyl acrylate (100.0 mg, 1.0 mmol) were added under argon, and the resulting mixture was stirred at 150°C for 48 hours. After cooling to room temperature, the solvent was evaporated under reduced pressure, and the product was separated by 300-400 mesh silica gel chromatography column with petroleum ether:ethyl acetate = 20:1 as the eluent. The product was dried in vacuo to obtain the product with a yield of 23% and an enantiomeric excess of 93%. 1 H NMR (500 MHz, CDCl3)δ 7.83(d, J = 8.5 Hz, 1H), 7.78 (d, J = 8.1 Hz, 1H), 7.36 – 7.29 (m, 5H), 7.20 (t, J =7.3 Hz, 1H), 7.17 – 7.11 (m, 5H), 7.11 – 7.05 (m, 2H), 7.00 – 6.90 (m, 3H), 4.07 (q, J = 7.2 Hz, 2H), 2.65 – 2.57 (m, 1H), 2.57 – 2.49 (m, 1H), 2.49 – 2.41(m, 1H), 2.39 – 2.31 (m, 1H), 1.21 (t, J= 7.2 Hz, 3H); 13 C NMR (126 MHz, CDCl3)δ172.7, 148.7 (d, J = 32.4 Hz), 140.7 (d, J = 16.8 Hz), 136.0 (d, J = 1.8 Hz), 135.9(d, J = 6.9 Hz), 135.5 (dd, J = 23.4, 11.8 Hz), 133.8 (d, J = 4.0 Hz), 133.6 (d, J =3.5 Hz), 132.4 (d, J = 2.3 Hz), 131.8, 131.3 (d, J = 5.2 Hz), 130.4 (q, J = 4.3Hz), 128.9, 128.7 (d, J = 12.1 Hz), 128.6 (d, J = 6.9 Hz), 128.3 (d, J = 7.5 Hz),127.7, 126.3, 125.9 (d, J = 12.1 Hz), 125.7 (q, J = 3.4 Hz), 125.1, 60.3, 35.0,28.7 (d, J = 2.9 Hz), 14.1; 31 P NMR (202 MHz, CDCl3)δ -16.02.

[0113] Example 40 Synthesis of Ethyl (R)-3-(1-(5-chloro-2-(diphenylphosphino)phenyl)naphthalen-2-yl)propionate

[0114] In a 25 mL dry Schlenk tube with a stir bar, (1,5-cyclooctadienyl)iridium(I) chloride dimer (3.4 mg, 0.01 mmol, 0.05 equiv) and (R)-(-)-(3,5-dioxo-4-phosphino-cycloheptyl[2,1-A,3,4-A']dinaphthyl)dimethylamine (8.0 mg, 0.022 mmol, 0.11 equiv) were added to 2.0 mL of toluene under Ar. The resulting mixed solution was stirred at room temperature for 1 h. Then, (4-chloro-2-(naphthalen-1-yl)phenyl)diphenylphosphine (84.4 mg, 0.2 mmol) and ethyl acrylate (100.0 mg, 1.0 mmol) were added under argon. The resulting mixture was stirred at 150°C for 48 hours. After cooling to room temperature, the solvent was evaporated under reduced pressure. The product was separated by 300-400 mesh silica gel chromatography column with petroleum ether:ethyl acetate = 20:1 as the eluent and dried in vacuo to obtain the product with a yield of 51% and an enantiomeric excess of 90%. 1 H NMR (500 MHz, CDCl3)δ 7.83(d, J = 8.6 Hz, 1H), 7.78 (d, J = 7.3 Hz, 1H), 7.40 – 7.32 (m, 3H), 7.31 – 7.27(m, 3H), 7.27 – 7.24 (m, 2H), 7.20 – 7.07 (m, 6H), 7.00 – 6.92 (m, 3H), 4.07(q, J = 7.0, 0.9 Hz, 2H), 2.67 – 2.51 (m, 2H), 2.50 – 2.42 (m, 1H), 2.40 – 2.31(m, 1H), 1.20 (t, J = 7.2 Hz, 3H); 13 C NMR (126 MHz, CDCl3) δ 172.8, 146.8 (d, J =34.5 Hz), 137.4 (d, J = 13.2 Hz), 136.4 (d, J = 5.5 Hz), 136.3 (d, J = 5.4 Hz),136.1 (d, J = 2.3 Hz), 135.9 (d, J = 6.8 Hz), 135.6 (d, J = 1.8 Hz), 135.4, 133.7(d,J = 3.6 Hz), 133.5 (d, J = 2.7 Hz), 132.7 (d, J = 2.3 Hz), 131.8, 130.7 (d, J =5.9 Hz), 128.6, 128.5 (d, J = 2.7 Hz), 128.3 (d, J = 19.5 Hz), 128.2 (d, J = 1.8Hz), 127.7, 126.3 (d, J = 12.7 Hz), 125.8, 125.1, 60.3, 35.0 (d, J = 1.8 Hz),28.8 (d, J = 2.3 Hz), 14.2; 31 P NMR (202 MHz, CDCl3)δ -16.63.

[0115] Example 41 Synthesis of Ethyl (R)-3-(4-chloro-1-(2-(diphenylphosphino)phenyl)naphthalen-2-yl)propionate

[0116] In a 25 mL dry Schlenk tube with a stir bar, (1,5-cyclooctadienyl)iridium(I) chloride dimer (3.4 mg, 0.01 mmol, 0.05 equiv) and (R)-(-)-(3,5-dioxo-4-phosphino-cycloheptyl[2,1-A,3,4-A']dinaphthyl)dimethylamine (8.0 mg, 0.022 mmol, 0.11 equiv) were added to 2.0 mL of toluene under Ar. The resulting mixed solution was stirred at room temperature for 1 h. Then, (2-(4-chloronaphthalen-1-yl)phenyl)diphenylphosphine (84.4 mg, 0.2 mmol) and ethyl acrylate (100.0 mg, 1.0 mmol) were added under argon. The resulting mixture was stirred at 150°C for 48 hours. After cooling to room temperature, the solvent was evaporated under reduced pressure. The product was separated by 300-400 mesh silica gel chromatography column with petroleum ether:ethyl acetate = 20:1 as the eluent and dried in vacuo to obtain the product with a yield of 75% and an enantiomeric excess of 93%. 1 H NMR (500 MHz, CDCl3)δ 8.22(d, J = 7.5 Hz, 1H), 7.50 – 7.46 (m, 2H), 7.43 (td, J= 7.6, 1.5 Hz, 2H), 7.34(ddd, J = 7.8, 3.6, 1.6 Hz, 1H), 7.32 – 7.28 (m, 3H), 7.24 – 7.21 (m, 1H), 7.21– 7.17 (m, 3H), 7.16 – 7.10 (m, 3H), 7.03 – 6.97 (m, 3H), 4.07 (q, J = 7.2 Hz,2H), 2.64 – 2.56 (m, 1H), 2.56 – 2.49 (m, 1H), 2.49 – 2.40 (m, 1H), 2.39 –2.31 (m, 1H), 1.21 (t, J = 7.1 Hz, 3H); 13 C NMR (126 MHz, CDCl3) δ 172.6, 144.2(d, J = 32.9 Hz), 138.5 (d, J = 12.1 Hz), 136.9 (d, J = 6.9 Hz), 136.61 (d, J = 9.2Hz), 136.55 (d, J = 1.8 Hz), 136.5, 134.3 (d, J = 1.7 Hz), 134.1 (d, J = 2.9 Hz),133.8 (d, J = 4.6 Hz), 133.7 (d, J = 3.5 Hz), 131.8, 130.9 (d, J = 5.8 Hz), 129.21,129.18, 128.5 (d, J = 6.4 Hz), 128.4 (d, J = 4.0 Hz), 128.1 (d, J = 2.9 Hz), 126.9(d, J = 31.2 Hz), 126.2 (d, J = 35.8 Hz), 124.1, 60.4, 34.9 (d, J = 2.3 Hz), 28.7(d, J = 2.9 Hz), 14.2; 31P NMR (202 MHz, CDCl3)δ -15.50.

[0117] Example 42 Synthesis of Ethyl (R)-3-(1-(2-(diphenylphosphino)-5-(trifluoromethyl)phenyl)naphthalen-2-yl)propionate

[0118] In a 25 mL dry Schlenk tube with a stir bar, (1,5-cyclooctadienyl)iridium(I) chloride dimer (3.4 mg, 0.01 mmol, 0.05 equiv) and (R)-(-)-(3,5-dioxo-4-phosphino-cycloheptyl[2,1-A,3,4-A']dinaphthyl)dimethylamine (8.0 mg, 0.022 mmol, 0.11 equiv) were added to 2.0 mL of toluene under Ar. The resulting mixed solution was stirred at room temperature for 1 h. Then, (2-(naphthalen-1-yl)-4-(trifluoromethyl)phenyl)diphenylphosphine (91.2 mg, 0.2 mmol) and ethyl acrylate (100.0 mg, 1.0 mmol) were added under argon, and the resulting mixture was stirred at 150°C for 48 hours. After cooling to room temperature, the solvent was evaporated under reduced pressure, and the product was separated by 300-400 mesh silica gel chromatography column with petroleum ether:ethyl acetate = 20:1 as the eluent. The product was dried in vacuo to obtain the product with a yield of 43% and an enantiomeric excess of 90%. 1 H NMR (500 MHz, CDCl3)δ 7.84 (d, J = 8.5 Hz, 1H), 7.78 (dd, J = 8.2, 1.5 Hz, 1H), 7.64 (dd, J = 8.2, 2.2Hz, 1H), 7.50 (dd, J = 3.8, 2.1 Hz, 1H), 7.43 (dd, J = 8.2, 3.0 Hz, 1H), 7.35 (d,1H), 7.33 – 7.28 (m, 4H), 7.20 – 7.16 (m, 2H), 7.16 – 7.07 (m, 4H), 7.00 –6.94 (m, 2H), 6.85 (d, J = 8.4 Hz, 1H), 4.05 (qd, J = 7.1, 1.3 Hz, 2H), 2.59 –2.50 (m, 2H), 2.50 – 2.42 (m, 1H), 2.42 – 2.33 (m, 1H), 1.18 (t, J= 7.1 Hz,3H) ; 13 C NMR (126 MHz, CDCl3)δ 172.7, 145.6 (d, J = 32.9 Hz), 144.1 (d, J = 16.8Hz), 136.3 (d, J = 2.3 Hz), 135.8, 135.7, 135.6, 135.5, 135.4, 134.4, 133.9 (d, J = 4.6 Hz), 133.8 (d, J = 3.5 Hz), 132.6 (d, J = 1.7 Hz), 131.9, 131.1 (q, J = 32.4Hz), 128.9, 128.8, 128.6 (d, J = 6.4 Hz), 128.3 (d, J = 7.5 Hz), 127.7, 127.4(dq, J = 7.6, 3.6 Hz), 126.4, 126.0, 125.9, 125.1, 124.5 (q, J = 3.4 Hz), 60.3,35.0 (d, J = 1.7 Hz), 28.8 (d, J = 2.3 Hz), 14.1; 31 P NMR (202 MHz, CDCl3)δ -15.19; 19 F NMR (471 MHz, CDCl3)δ -62.59.

[0119] Example 43 Synthesis of Ethyl (R)-3-(1-(2-(diphenylphosphino)-4-(trifluoromethyl)phenyl)naphthalen-2-yl)propionate

[0120] In a 25 mL dry Schlenk tube with a stir bar, (1,5-cyclooctadienyl)iridium(I) chloride dimer (3.4 mg, 0.01 mmol, 0.05 equiv) and (R)-(-)-(3,5-dioxo-4-phosphino-cycloheptyl[2,1-A,3,4-A']dinaphthyl)dimethylamine (8.0 mg, 0.022 mmol, 0.11 equiv) were added to 2.0 mL of toluene under Ar. The resulting mixed solution was stirred at room temperature for 1 h. Then, (2-(naphthalen-1-yl)-5-(trifluoromethyl)phenyl)diphenylphosphine (91.2 mg, 0.2 mmol) and ethyl acrylate (100.0 mg, 1.0 mmol) were added under argon, and the resulting mixture was stirred at 150°C for 48 hours. After cooling to room temperature, the solvent was evaporated under reduced pressure, and the product was separated by 300-400 mesh silica gel chromatography column with petroleum ether:ethyl acetate = 20:1 as the eluent. The product was dried in vacuo to obtain the product with a yield of 48% and an enantiomeric excess of 99%. 1 H NMR (500 MHz, CDCl3)δ7.84 (d, J = 8.6 Hz, 1H), 7.77 (d, J = 7.9 Hz, 1H), 7.71 (dd, J = 7.9, 2.2 Hz, 1H),7.57 (s, 1H), 7.39 – 7.34 (m, 2H), 7.34 – 7.27 (m, 4H), 7.20 – 7.14 (m, 3H),7.13 – 7.06 (m, 3H), 6.96 (t, J = 7.4 Hz, 2H), 6.85 (d, J = 8.5 Hz, 1H), 4.05 (q, J = 7.2 Hz, 2H), 2.59 – 2.49 (m, 2H), 2.48 – 2.40 (m, 1H), 2.40 – 2.31 (m,1H), 1.18 (t, J = 7.2 Hz, 3H); 13 C NMR (126 MHz, CDCl3) δ 172.7, 148.8 (d, J = 32.4Hz), 140.8 (d, J = 16.8 Hz), 136.0 (d, J = 2.3 Hz), 135.9 (d, J= 6.9 Hz), 135.6(d, J = 12.1 Hz), 135.4 (d, J = 12.1 Hz), 133.9 (d, J = 3.5 Hz), 133.7 (d, J = 2.3Hz), 132.5 (d, J = 2.3 Hz), 131.9, 131.4 (d, J = 5.2 Hz), 130.4 (q, J = 4.7, 4.2Hz), 130.11 (d, J = 32.2 Hz), 128.9 (d, J = 11.6 Hz), 128.7, 128.6 (d, J = 6.9 Hz),128.3 (d, J = 7.5 Hz), 127.7, 126.4, 126.0 (d, J = 12.1 Hz), 125.8 (q, J = 3.5Hz), 125.2, 60.4, 35.0, 28.8 (d, J = 2.9 Hz), 14.2; 31 P NMR (202 MHz, CDCl3)δ -14.84; 19 F NMR (471 MHz, CDCl3)δ -108.22.

[0121] Example 44 Synthesis of Ethyl (R)-3-(5-(2-(diphenylphosphino)phenyl)-1,2-dihydroacenaphthen-4-yl)propionate

[0122] In a 25 mL dry Schlenk tube with a stir bar, (1,5-cyclooctadienyl)iridium(I) chloride dimer (3.4 mg, 0.01 mmol, 0.05 equiv) and (R)-(-)-(3,5-dioxo-4-phosphino-cycloheptyl[2,1-A,3,4-A']dinaphthyl)dimethylamine (8.0 mg, 0.022 mmol, 0.11 equiv) were added to 2.0 mL of m-xylene under Ar. The resulting mixed solution was stirred at room temperature for 1 h. Then, (2-(1,2-dihydroacenaphthen-5-yl)phenyl)diphenylphosphine (82.8 mg, 0.2 mmol) and ethyl acrylate (100.0 mg, 1.0 mmol) were added under argon, and the resulting mixture was stirred at 150°C for 48 hours. After cooling to room temperature, the solvent was evaporated under reduced pressure, and the product was separated by 300-400 mesh silica gel chromatography column with petroleum ether:ethyl acetate = 20:1 as the eluent. The product was dried in vacuo to obtain the product with a yield of 61% and an enantiomeric excess of 93%. 1 H NMR (500 MHz, CDCl3)δ 7.44 (td, J = 7.5, 1.7 Hz, 1H), 7.37 (td, J = 7.6, 1.5 Hz, 1H), 7.34 – 7.30 (m,1H), 7.27 (dd, J = 4.4, 2.3 Hz, 3H), 7.25 – 7.20 (m, 2H), 7.20 – 7.16 (m, 2H), 7.16 – 7.11 (m, 5H), 7.04 (td, J = 7.8, 1.7 Hz, 2H), 6.73 (dd, J = 6.6, 2.4 Hz,1H), 4.03 (q, J = 7.1 Hz, 2H), 3.46 – 3.29 (m, 4H), 2.66 – 2.58 (m, 1H), 2.58 –2.50 (m, 1H), 2.45 – 2.37 (m, 1H), 2.34 – 2.25 (m, 1H), 1.18 (t, J = 7.2 Hz,3H); 13 C NMR (126 MHz, CDCl3) δ 173.0, 145.7 (d, J = 66.5 Hz), 145.1 (d, J = 33.5Hz), 138.4 (d,J = 11.0 Hz), 138.0 (d, J = 2.9 Hz), 137.8, 137.6 (d, J = 12.7 Hz),137.2, 134.5 (d, J = 2.9 Hz), 133.8 (d, J = 19.7 Hz), 133.6 (d, J = 20.2 Hz), 133.2(d, J = 7.5 Hz), 131.4 (d, J = 2.3 Hz), 131.1 (d, J = 5.8 Hz), 129.2, 128.4, 128.3(d, J = 17.9 Hz), 128.1 (d, J = 6.9 Hz), 127.7 (d, J = 2.3 Hz), 121.5, 120.1,118.7, 60.2, 35.6, 30.6, 30.2, 29.3(d, J = 2.3 Hz), 14.3; 31 P NMR (202 MHz, CDCl3)δ -15.59.

[0123] Example 45 Synthesis of Ethyl (R)-3-(10-(2-(diphenylphosphino)phenyl)phenanthren-9-yl)propionate

[0124] In a 25 mL dry Schlenk tube with a stir bar, (1,5-cyclooctadienyl)iridium(I) chloride dimer (3.4 mg, 0.01 mmol, 0.05 equiv) and (R)-(-)-(3,5-dioxo-4-phosphino-cycloheptyl[2,1-A,3,4-A']dinaphthyl)dimethylamine (8.0 mg, 0.022 mmol, 0.11 equiv) were added to 2.0 mL of toluene under Ar. The resulting mixed solution was stirred at room temperature for 1 h. Then, (2-(phenanthren-9-yl)phenyl)diphenylphosphine (87.6 mg, 0.2 mmol) and ethyl acrylate (100.0 mg, 1.0 mmol) were added under argon. The resulting mixture was stirred at 150°C for 48 hours. After cooling to room temperature, the solvent was evaporated under reduced pressure. The product was separated by 300-400 mesh silica gel chromatography column with petroleum ether:ethyl acetate = 20:1 as the eluent and dried in vacuo to obtain the product with a yield of 51% and an enantiomeric excess of 90%. 1H NMR (500 MHz, CDCl3)δ 8.03 (d, J =7.6 Hz, 1H), 7.47 (td, J = 7.5, 1.7 Hz, 1H), 7.41 (td, J = 7.6, 1.6 Hz, 1H), 7.39– 7.35 (m, 1H), 7.34 – 7.26 (m, 5H), 7.25 – 7.15 (m, 5H), 7.15 – 7.10 (m,3H), 7.04 (d, J = 11.6 Hz, 1H), 7.02 – 6.97 (m, 2H), 6.95 (d, J = 8.5 Hz, 1H),4.06 (q, J = 7.2 Hz, 2H), 2.63 – 2.56 (m, 1H), 2.54 – 2.47 (m, 1H), 2.46 – 2.39(m, 1H), 2.36 – 2.29 (m, 1H), 1.20 (t, J = 7.1 Hz, 3H).; 13 C NMR (126 MHz, CDCl3)δ 172.7, 159.5, 157.5, 144.3 (d, J = 32.9 Hz), 138.8 (d, J = 11.6 Hz), 136.7 (d, J = 4.6 Hz), 136.6 (d, J = 4.6 Hz), 134.2, 133.8 (d, J = 1.4 Hz), 133.6 (d, J = .2Hz), 131.1 (d, J = 5.8 Hz), 129.1, 128.44, 128.38, 128.36, 128.3, 128.12,128.07, 128.0, 126.5, 126.4 (d, J = 3.5 Hz), 125.2 (d, J = 1.2 Hz), 122.1 (d, J =16.8 Hz), 120.1 (d, J = 5.2 Hz), 109.8 (d, J= 19.7 Hz), 60.3, 34.8, 28.8, 14.2; 31 P NMR (202 MHz, CDCl3)δ -15.33.

[0125] Example 46 Synthesis of Ethyl (R)-3-(1-(2-(diphenylphosphino)phenyl)pyrene-2-yl)propionate

[0126] In a 25 mL dry Schlenk tube with a stir bar, (1,5-cyclooctadienyl)iridium(I) chloride dimer (3.4 mg, 0.01 mmol, 0.05 equiv) and (R)-(-)-(3,5-dioxo-4-phosphino-cycloheptyl[2,1-A,3,4-A']dinaphthyl)dimethylamine (8.0 mg, 0.022 mmol, 0.11 equiv) were added to 2.0 mL of toluene under Ar. The resulting mixed solution was stirred at room temperature for 1 h. Diphenyl(2-(pyrene-1-yl)phenyl)phosphine (92.4 mg, 0.2 mmol) and ethyl acrylate (100.0 mg, 1.0 mmol) were then added under argon. The resulting mixture was stirred at 150°C for 48 hours. After cooling to room temperature, the solvent was evaporated under reduced pressure. The product was separated by 300-400 mesh silica gel chromatography column with petroleum ether:ethyl acetate = 20:1 as the eluent and dried in vacuo to obtain the product in a yield of 58% and an enantiomeric excess of 86%. 1 H NMR (500 MHz, CDCl3)δ 8.16 (d, J =7.6 Hz, 1H), 8.11 – 8.02 (m, 4H), 7.95 (t, J = 7.5 Hz, 1H), 7.63 (d, J = 9.2 Hz,1H), 7.54 (t, J = 7.4 Hz, 1H), 7.49 (t, J = 7.6 Hz, 1H), 7.41 (dd, J = 7.7, 3.6 Hz,1H), 7.38 – 7.34 (m, 1H), 7.32 – 7.27 (m, 3H), 7.22 – 7.16 (m, 3H), 7.16 –7.11 (m, 1H), 7.08 – 7.01 (m, 2H), 6.96 (t, J = 7.7 Hz, 2H), 4.09 (q, J= 7.1 Hz,2H), 2.99 – 2.90 (m, 2H), 2.70 – 2.61 (m, 1H), 2.58 – 2.49 (m, 1H), 1.21 (t, J = 7.1 Hz, 3H); 13 C NMR (126 MHz, CDCl3)δ 173.0, 145.3 (d, J = 32.9 Hz), 138.8(d, J = 12.1 Hz), 136.9 (d, J = 12.1 Hz), 136.7 (d, J = 1.4 Hz), 136.4, 136.32,136.26, 134.2 (d, J = 1.7 Hz), 133.9 (d, J = 20.8 Hz), 133.6 (d, J = 19.7 Hz),131.2 (d, J = 5.8 Hz), 131.0 (d, J = 19.1 Hz), 130.5, 130.1 (d, J = 2.3 Hz), 129.1,128.33, 128.32, 128.28, 128.1 (d, J = 6.9 Hz), 128.0, 127.3 (d, J = 17.3 Hz),126.8, 125.7 (d, J = 17.9 Hz), 124.8 (d, J = 12.7 Hz), 124.6, 124.4, 123.1, 60.3,35.4, 29.3 (d, J = 2.9 Hz), 14.2; 31 P NMR (202 MHz, CDCl3)δ -15.27.

[0127] Example 47 Synthesis of Ethyl (R)-3-(3'-(diphenylphosphino)-[1,2'-binaphthyl]-2-yl) Propionate

[0128] In a 25 mL dry Schlenk tube with a stir bar, (1,5-cyclooctadienyl)iridium(I) chloride dimer (3.4 mg, 0.01 mmol, 0.05 equiv) and (R)-(-)-(3,5-dioxo-4-phosphino-cycloheptyl[2,1-A,3,4-A']dinaphthyl)dimethylamine (8.0 mg, 0.022 mmol, 0.11 equiv) were added to 2.0 mL of toluene under Ar. The resulting mixed solution was stirred at room temperature for 1 h. Then, [1,2'-binaphthyl]-3'-diphenylphosphine (87.6 mg, 0.2 mmol) and ethyl acrylate (100.0 mg, 1.0 mmol) were added under argon. The resulting mixture was stirred at 150°C for 48 hours. After cooling to room temperature, the solvent was evaporated under reduced pressure. The product was separated by 300-400 mesh silica gel chromatography column with petroleum ether:ethyl acetate = 20:1 as the eluent and dried in vacuo to obtain the product with a yield of 78% and an enantiomeric excess of 91%. 1 H NMR (500 MHz, CDCl3)δ 7.82 (t, J = 9.2Hz, 1H), 7.79 – 7.73 (m, 3H), 7.71 (d, J = 4.1 Hz, 1H), 7.55 – 7.45 (m, 2H), 7.37 (d, J = 8.4 Hz, 1H), 7.34 – 7.25 (m, 4H), 7.25 – 7.18 (m, 2H), 7.15 (t, J =7.2 Hz, 1H), 7.09 (t, J = 7.6 Hz, 2H), 7.05 – 6.97 (m, 3H), 6.95 (d, J = 8.4 Hz,1H), 4.01 (q, J = 7.1 Hz, 2H), 2.65 – 2.51 (m, 2H), 2.50 – 2.42 (m, 1H), 2.41 –2.33 (m, 1H), 1.14 (t, J = 7.2 Hz, 3H); 13 C NMR (126 MHz, CDCl3) δ 172.9, 141.2(d, J = 32.4 Hz), 137.5 (d, J = 13.3 Hz), 136.8 (d, J = 6.4 Hz), 136.6 (d, J= 1.8Hz), 136.5 (d, J = 11.6 Hz), 136.3 (d, J = 11.6 Hz), 134.4, 134.0 (d, J = 10.4 Hz),133.9 (d, J = 11.6 Hz), 133.4, 133.3 (d, J = 2.9 Hz), 132.7, 131.8, 129.5 (d, J =5.8 Hz), 128.5, 128.4, 128.3 (d, J = 9.2 Hz), 128.1 (d, J = 3.5 Hz), 128.0, 127.6(d, J = 24.9 Hz), 127.0, 126.6, 126.3 (d, J = 29.5 Hz), 125.5, 124.8, 60.2, 35.1,28.9 (d, J = 2.9 Hz), 14.1; 31 P NMR (202 MHz, CDCl3)δ -14.28.

[0129] Example 48 Synthesis of Ethyl (S)-3-(4-(2-(diphenylphosphino)phenyl)quinolin-3-yl)propionate

[0130] In a 25 mL dry Schlenk tube with a stir bar, (1,5-cyclooctadienyl)iridium(I) chloride dimer (3.4 mg, 0.01 mmol, 0.05 equiv) and (R)-(-)-(3,5-dioxo-4-phosphino-cycloheptyl[2,1-A,3,4-A']dinaphthyl)dimethylamine (8.0 mg, 0.022 mmol, 0.11 equiv) were added to 2.0 mL of toluene under Ar. The resulting mixed solution was stirred at room temperature for 1 h. 4-(2-(diphenylphosphino)phenyl)quinoline (77.8 mg, 0.2 mmol) and ethyl acrylate (100.0 mg, 1.0 mmol) were then added under argon. The resulting mixture was stirred at 150°C for 48 hours. After cooling to room temperature, the solvent was evaporated under reduced pressure. The product was separated by 300-400 mesh silica gel chromatography column with petroleum ether:ethyl acetate = 20:1 as the eluent and dried in vacuo to obtain the product in a yield of 48% and an enantiomeric excess of 91%. 1H NMR (500 MHz, CDCl3) δ8.82 (s,1H), 8.05 (d, J = 8.4 Hz, 1H), 7.54 (ddd, J = 8.4, 6.8, 1.4 Hz, 1H), 7.50 (td, J =7.5, 1.6 Hz, 1H), 7.45 (td, J = 7.5, 1.5 Hz, 1H), 7.34 (ddd, J = 7.6, 3.5, 1.5Hz, 1H), 7.32 – 7.27 (m, 3H), 7.22 – 7.16 (m, 4H), 7.15 – 7.11 (m, 3H), 7.02– 6.94 (m, 3H), 4.06 (q, J = 7.1 Hz, 2H), 2.71 – 2.65 (m, 2H), 2.52 – 2.45 (m,1H), 2.42 – 2.34 (m, 1H), 1.20 (t, J = 7.2 Hz, 3H); 13 C NMR (126 MHz, CDCl3) δ 172.4, 151.5, 146.6, 145.9 (d, J = 6.4 Hz), 142.1 (d, J = 32.9 Hz), 137.7 (d, J =14.4 Hz), 136.2 (d, J = 11.6 Hz), 135.9 (d, J = 11.6 Hz), 134.3, 133.9, 133.8,133.6, 131.0, 130.0 (d, J = 6.4 Hz), 129.2, 129.1, 128.6 (d, J = 2.3 Hz), 128.64(d, J = 5.2 Hz), 128.56 (d, J = 5.2 Hz), 128.2 (d, J = 6.9 Hz), 127.7 (d, J = 2.9Hz), 126.2 (d, J = 11.6 Hz), 60.5, 34.7, 26.4 (d,J = 2.9 Hz), 14.2; 31 P NMR (202MHz, CDCl3)δ -15.15.

[0131] Example 49 Synthesis of Ethyl (R)-3-(1-(2-(diphenylphosphino)phenyl)dibenzo[b,d]furan-2-yl)propionate

[0132] In a 25 mL dry Schlenk tube with a stir bar, (1,5-cyclooctadienyl)iridium(I) chloride dimer (3.4 mg, 0.01 mmol, 0.05 equiv) and (R)-(-)-(3,5-dioxo-4-phosphino-cycloheptyl[2,1-A,3,4-A']dinaphthyl)dimethylamine (8.0 mg, 0.022 mmol, 0.11 equiv) were added to 2.0 mL of toluene under Ar. The resulting mixed solution was stirred at room temperature for 1 h. Then, (2-(dibenzo[b,d]furan-1-yl)phenyl)diphenylphosphine (85.6 mg, 0.2 mmol) and ethyl acrylate (100.0 mg, 1.0 mmol) were added under argon. The resulting mixture was stirred at 150°C for 48 hours. After cooling to room temperature, the solvent was evaporated under reduced pressure. The product was separated by 300-400 mesh silica gel chromatography column with petroleum ether:ethyl acetate = 20:1 as the eluent and dried in vacuo to obtain the product with a yield of 57% and an enantiomeric excess of 90%. 1 H NMR (500 MHz, CDCl3) δ7.53 – 7.47 (m, 2H), 7.47 – 7.41 (m, 2H), 7.36 – 7.31 (m, 2H), 7.31 – 7.26(m, 5H), 7.24 – 7.19 (m, 2H), 7.01 – 6.96 (m, 1H), 6.95 – 6.87 (m, 5H), 6.35– 6.29 (m, 1H), 4.05 (q, J = 7.2 Hz, 2H), 2.71 – 2.63 (m, 1H), 2.60 – 2.52 (m,1H), 2.48 – 2.40 (m, 1H), 2.34 – 2.25 (m, 1H), 1.18 (t, J = 7.2 Hz, 3H); 13 C NMR(126 MHz, CDCl3)δ 172.9, 156.3, 154.3, 144.0 (d, J = 32.4 Hz), 138.1(d, J= 13.3Hz), 136.3 (d, J = 11.6 Hz), 136.1 (d, J = 11.6 Hz), 135.4 (d, J = 7.5 Hz), 134.0,133.9, 133.7, 133.1, 129.9 (d, J = 5.2 Hz), 129.5, 128.5 (d, J = 13.9 Hz), 128.4(d, J = 2.9 Hz), 128.2, 127.9 (d, J = 6.9 Hz), 127.4, 126.5, 124.4, 123.6 (d, J =2.9 Hz), 122.1(d, J = 2.9 Hz), 111.0 (d, J = 28.9 Hz), 60.2, 35.6, 27.6 (d, J = 3.5Hz), 14.2; 31 P NMR (202 MHz, CDCl3)δ -14.16.

[0133] Example 50 Synthesis of Ethyl (R)-3-(1-(2-(bis(4-fluorophenyl)phosphino)phenyl)naphthalen-2-yl)propionate

[0134] In a 25.0 mL dry Schlenk tube with a stir bar, di(ethylene)iridium chloride dimer (3.4 mg, 0.01 mmol, 0.05 equiv) and (R)-(-)-(3,5-dioxo-4-phosphino-cycloheptyl[2,1-A,3,4-A']dinaphthyl)dimethylamine (8.0 mg, 0.022 mmol, 0.11 equiv) were added to 2.0 mL of p-xylene under Ar. The resulting mixed solution was stirred at room temperature for 1 h. Then, bis(4-fluorophenyl)(2-(naphthalen-1-yl)phenyl)phosphine (84.8 mg, 0.2 mmol) and ethyl acrylate (100.0 mg, 1.0 mmol) were added under argon, and the resulting mixture was stirred at 150°C for 48 hours. After cooling to room temperature, the solvent was evaporated under reduced pressure, and the product was separated by 300-400 mesh silica gel chromatography column with petroleum ether:ethyl acetate = 20:1 as the eluent. The product was dried in vacuo to obtain the product with a yield of 40% and an enantiomeric excess of 95%. 1 H NMR (500 MHz, CDCl3) δ 7.82 (d, J=8.5 Hz, 1H), 7.77 (d, J = 7.6 Hz, 1H), 7.49 (td, J = 7.5, 1.4 Hz, 1H), 7.43 (td, J = 7.6, 1.6 Hz, 1H), 7.37 (d, J = 8.4 Hz, 1H), 7.34 – 7.30 (m, 1H), 7.26 – 7.22(m, 2H), 7.18 – 7.12 (m, 2H), 7.10 – 7.05 (m, 1H), 7.00 (t, J = 8.4 Hz, 2H),6.96 – 6.90 (m, 2H), 6.88 (d, J = 8.4 Hz, 1H), 6.81 (t, J = 8.8 Hz, 2H), 4.11 –4.01 (m, 2H), 2.68 – 2.55 (m, 2H), 2.52 – 2.43 (m, 1H), 2.40 – 2.32 (m, 1H),1.20 (t, J = 7.2 Hz, 3H); 13 C NMR (126 MHz, CDCl3) δ 172.8, 163.1 (d, J = 248.5Hz), 144.8 (d, J = 32.9 Hz), 138.2 (d, J = 12.1 Hz), 137.0 (d, J = 7.5 Hz), 136.0(d, J = 1.6 Hz), 135.7 (d, J = 8.1 Hz), 135.5 (d, J = 8.0 Hz), 135.4 (d, J = 7.9Hz), 133.6, 132.9 (d, J = 2.0 Hz), 132.1 (dd, J = 12.3, 3.4 Hz), 131.9 (dd, J =12.3, 3.4 Hz), 131.8, 131.0 (d, J = 5.6 Hz), 129.3, 128.1 (d, J= 31.2 Hz),127.6, 126.4 (d, J = 23.1 Hz), 125.3 (d, J = 76.9 Hz), 115.6 (dd, J = 20.8, 7.5Hz), 115.3 (dd, J = 21.1, 7.8 Hz), 60.3, 35.1, 28.9 (d, J = 2.9 Hz), 14.1; 31 P NMR(202 MHz, CDCl3)δ -17.50; 19 F NMR (471 MHz, CDCl3)δ -112.66 (d, J = 4.3 Hz), -112.79 (d, J = 4.3 Hz).

[0135] Example 51 Synthesis of Ethyl (R)-3-(1-(2-(di(thiophen-2-yl)phosphino)phenyl)naphthalen-2-yl)propionate

[0136] In a 25 mL dry Schlenk tube with a stir bar, (1,5-cyclooctadienyl)iridium(I) chloride dimer (3.4 mg, 0.01 mmol, 0.05 equiv) and (R)-(-)-(3,5-dioxo-4-phosphino-cycloheptyl[2,1-A,3,4-A']dinaphthyl)dimethylamine (8.0 mg, 0.022 mmol, 0.11 equiv) were added to 2.0 mL of toluene under Ar. The resulting mixed solution was stirred at room temperature for 1 h. Then, (2-(naphthalen-1-yl)phenyl)di(thiophen-2-yl)phosphine (80.0 mg, 0.2 mmol) and ethyl acrylate (100.0 mg, 1.0 mmol) were added under argon, and the resulting mixture was stirred at 150°C for 48 hours. After cooling to room temperature, the solvent was evaporated under reduced pressure, and the product was separated by 300-400 mesh silica gel chromatography column with petroleum ether:ethyl acetate = 20:1 as the eluent. The product was dried in vacuo to obtain the product with a yield of 37% and an enantiomeric excess of 87%. 1 H NMR (500 MHz, CDCl3) δ 7.84(d, J = 8.4 Hz, 1H), 7.79 (d, J = 8.1 Hz, 1H), 7.63 – 7.58 (m, 1H), 7.55 (d, J=5.0 Hz, 1H), 7.51 – 7.44 (m, 2H), 7.42 – 7.37 (m, 2H), 7.36 – 7.31 (m, 1H),7.25 – 7.20 (m, 1H), 7.14 – 7.08 (m, 2H), 7.08 – 7.04 (m, 1H), 6.98 (d, J = 8.5Hz, 1H), 6.83 – 6.79 (m, 1H), 6.76 (dd, J = 6.5, 3.1 Hz, 1H), 4.06 (q, J = 7.1Hz, 2H), 2.66 (t, J = 8.1 Hz, 2H), 2.51 – 2.35 (m, 2H), 1.19 (t, J = 7.1 Hz, 3H); 13 C NMR (126 MHz, CDCl3) δ 172.9, 143.7 (d, J = 34.1 Hz), 139.0 (d, J = 7.5 Hz),137.8 (d, J = 24.9 Hz), 137.6 (d, J = 25.4 Hz), 136.8 (d, J = 6.9 Hz), 136.3, 135.6(d, J = 21.4 Hz), 135.4 (d, J = 22.0 Hz), 133.0 (d, J = 2.9 Hz), 132.8, 131.8,131.5 (d, J = 37.0 Hz), 130.7 (d, J = 5.8 Hz), 129.4, 128.2 (d, J = 33.5 Hz), 127.9(d, J = 7.5 Hz), 127.6, 127.5, 126.6, 126.2, 125.6, 124.9, 60.2, 35.2 , 28.8(d, J = 2.9 Hz), 14.2; 31 P NMR (202 MHz, CDCl3)δ -43.41; 19F NMR (471 MHz, CDCl3)δ-112.66 (d, J = 4.3 Hz), -112.79 (d, J = 4.3 Hz).

[0137] Example 52 Synthesis of Methyl (R)-3-(1-(2-(diphenylphosphino)phenyl)naphthalen-2-yl)propionate

[0138] In a 25 mL dry Schlenk tube with a stir bar, iridium(I) bis(1,5-cyclooctadiene)tetrafluoroborate (3.4 mg, 0.01 mmol, 0.05 equiv) and (R)-(-)-(3,5-dioxo-4-phosphino-cycloheptyl[2,1-A,3,4-A']dinaphthyl)dimethylamine (8.0 mg, 0.022 mmol, 0.11 equiv) were added to 2.0 mL of toluene under Ar. The resulting mixed solution was stirred at room temperature for 1 h. Then, (2-(naphthalen-1-yl)phenyl)diphenylphosphine (77.6 mg, 0.2 mmol) and methyl acrylate (86.0 mg, 1.0 mmol) were added under argon. The resulting mixture was stirred at 150°C for 48 hours. After cooling to room temperature, the solvent was evaporated under reduced pressure. The product was separated by 300-400 mesh silica gel chromatography column with petroleum ether:ethyl acetate = 20:1 as the eluent and dried in vacuo to obtain the product with a yield of 77% and an enantiomeric excess of 82%. 1 H NMR (400 MHz, CDCl3) δ 7.81 (d, J =8.5 Hz, 1H), 7.76 (d, J = 8.2 Hz, 1H), 7.46 (td, J = 7.3, 1.6 Hz, 1H), 7.40 (td, J = 7.5, 1.6 Hz, 1H), 7.32 (td, J = 8.7, 1.7 Hz, 3H), 7.30 – 7.25 (m, 3H), 7.25 –7.21 (m, 1H), 7.21 – 7.16 (m, 2H), 7.15 – 7.12 (m, 1H), 7.12 – 7.07 (m, 2H),7.03 – 6.94 (m, 3H), 3.58 (s, 3H), 2.66 – 2.58 (m, 1H), 2.57 – 2.49 (m, 1H), 2.48 – 2.41 (m, 1H), 2.38 – 2.28 (m, 1H); 13C NMR (101 MHz, CDCl3) δ 173.3,145.0 (d, J = 33.2 Hz), 138.3 (d, J = 12.3 Hz), 137.4 (d, J = 6.8 Hz), 136.9 (d, J =8.2 Hz), 136.8 (d, J = 8.6 Hz), 135.9, 134.3, 133.7 (d, J = 5.9 Hz), 133.5 (d, J =6.4 Hz), 133.0, 131.8, 130.8 (d, J = 5.9 Hz), 129.1, 128.3, 128.2 (d, J = 2.3Hz), 128.1 (d, J = 6.8 Hz), 128.0, 127.7 (d, J = 28.6 Hz), 126.4 (d, J = 10.0Hz), 125.2 (d, J = 64.9 Hz), 51.4, 34.8, 28.8; 31 P NMR (162 MHz, CDCl3)δ -15.45.

[0139] Example 53 Synthesis of tert-butyl (R)-3-(1-(2-(diphenylphosphino)phenyl)naphthalen-2-yl)propionate

[0140] In a 25 mL dry Schlenk tube with a stir bar, (1,5-cyclooctadienyl)iridium(I) chloride dimer (3.4 mg, 0.01 mmol, 0.05 equiv) and (R)-(-)-(3,5-dioxo-4-phosphino-cycloheptyl[2,1-A,3,4-A']dinaphthyl)dimethylamine (8.0 mg, 0.022 mmol, 0.11 equiv) were added to 2.0 mL of toluene under Ar. The resulting mixed solution was stirred at room temperature for 1 h. Then, (2-(naphthalen-1-yl)phenyl)diphenylphosphine (77.6 mg, 0.2 mmol) and tert-butyl acrylate (128.2 mg, 1.0 mmol) were added under argon. The resulting mixture was stirred at 150°C for 48 hours. After cooling to room temperature, the solvent was evaporated under reduced pressure. The product was separated by 300-400 mesh silica gel chromatography column with petroleum ether:ethyl acetate = 20:1 as the eluent and dried in vacuo to obtain the product with a yield of 59% and an enantiomeric excess of 92%. 1 H NMR (500 MHz, CDCl3) δ 7.83(d, J = 8.5 Hz, 1H), 7.78 (d, J = 7.9 Hz, 1H), 7.48 (td, J = 7.5, 1.6 Hz, 1H), 7.42(td, J = 7.6, 1.7 Hz, 1H), 7.38 – 7.32 (m, 3H), 7.31 – 7.28 (m, 3H), 7.26 –7.23 (m, 1H), 7.21 – 7.16 (m, 3H), 7.16 – 7.11 (m, 2H), 7.11 – 7.06 (m, 1H),7.04 – 6.96 (m, 3H), 4.04 – 3.97 (m, 2H), 2.65 – 2.52 (m, 2H), 2.50 – 2.41(m, 1H), 2.40 – 2.32 (m, 1H), 1.57 – 1.49 (m, 2H), 1.33 – 1.28 (m, 2H), 0.89(t, J = 7.4 Hz, 3H); 13 C NMR (126 MHz, CDCl3) δ 173.0, 145.0 (d, J = 33.5 Hz),138.4 (d, J = 12.1 Hz), 137.4 (d, J = 7.5 Hz), 136.9 (d,J = 12.7 Hz), 136.1 (d, J =2.3 Hz), 134.2 (d, J = 2.3 Hz), 133.8 (d, J = 2.9 Hz), 133.6 (d, J = 2.9 Hz), 133.0(d, J = 2.3 Hz), 131.8, 130.8 (d, J = 5.8 Hz), 129.1, 128.31 (d, J = 1.5 Hz),128.25 (d, J = 1.5 Hz), 128.1 (d, J = 5.2 Hz), 128.0, 127.8, 127.5, 126.5 (d, J =2.9 Hz), 125.5, 124.9, 64.2, 35.2, 30.6, 28.9 (d, J = 2.9 Hz), 19.1, 13.7; 31 PNMR (202 MHz, CDCl3)δ -15.40.

[0141] Example 542, Synthesis of 2,2-trifluoroethyl (R)-3-(1-(2-(diphenylphosphino)phenyl)naphthalen-2-yl)propionate

[0142] In a 25 mL dry Schlenk tube with a stir bar, (1,5-cyclooctadienyl)iridium(I) chloride dimer (3.4 mg, 0.01 mmol, 0.05 equiv) and (R)-(-)-(3,5-dioxo-4-phosphino-cycloheptyl[2,1-A,3,4-A']dinaphthyl)dimethylamine (8.0 mg, 0.022 mmol, 0.11 equiv) were added to 2.0 mL of toluene under Ar. The resulting mixed solution was stirred at room temperature for 1 h. Then, (2-(naphthalen-1-yl)phenyl)diphenylphosphine (77.6 mg, 0.2 mmol) and trifluoroethyl acrylate (154.1 mg, 1.0 mmol) were added under argon. The resulting mixture was stirred at 150°C for 48 hours. After cooling to room temperature, the solvent was evaporated under reduced pressure. The product was separated by 300-400 mesh silica gel chromatography column with petroleum ether:ethyl acetate = 20:1 as the eluent and dried in vacuo to obtain the product with a yield of 51% and an enantiomeric excess of 93%. 1 H NMR (500 MHz, CDCl3)δ 7.81 (d,J = 8.5 Hz, 1H), 7.77 (d, J = 8.1 Hz, 1H), 7.49 – 7.44 (m, 1H), 7.40 (td, J = 7.6,1.7 Hz, 1H), 7.36 – 7.30 (m, 3H), 7.29 – 7.25 (m, 3H), 7.24 – 7.21 (m, 1H),7.19 – 7.14 (m, 3H), 7.13 – 7.08 (m, 3H), 7.02 – 6.97 (m, 3H), 4.36 (qd, J =8.5, 1.4 Hz, 2H), 2.69 – 2.60 (m, 1H), 2.59 – 2.49 (m, 2H), 2.45 – 2.36 (m,1H); 13 C NMR (126 MHz, CDCl3) δ 171.2, 144.8 (d, J = 32.9 Hz), 138.4 (d, J = 12.1Hz), 137.5 (d, J = 7.5 Hz), 136.8 (d, J = 12.1 Hz), 136.6 (d, J = 12.7 Hz), 135.3(d, J = 2.9 Hz), 134.3 (d, J = 2.3 Hz), 133.8 (d, J = 15.6 Hz), 133.6 (d, J = 16.8Hz), 133.0 (d, J = 2.3 Hz), 131.9, 130.7 (d, J = 5.8 Hz), 129.1, 128.4 (d, J = 6.9Hz), 128.32, 128.27, 128.1 (d, J = 6.9 Hz), 127.9, 127.6, 126.5, 126.2, 125.7,125.1, 122.9 (q, J = 276.9 Hz), 60.2 (q, J = 36.4 Hz), 34.3, 28.5 (d, J= 2.3 Hz); 31 P NMR (202 MHz, CDCl3)δ -15.45; 19 F NMR (471 MHz, CDCl3)δ -73.66.

[0143] Example 55 Synthesis of Ethyl (R)-3-(2'-(diphenylphosphino)-[1,1'-binaphthyl]-2-yl) Propionate

[0144] In a 25 mL dry Schlenk tube with a stir bar, (1,5-cyclooctadienyl)iridium(I) chloride dimer (3.4 mg, 0.01 mmol, 0.05 equiv) and (R)-(-)-(3,5-dioxo-4-phosphino-cycloheptyl[2,1-A,3,4-A']dinaphthyl)dimethylamine (8.0 mg, 0.022 mmol, 0.11 equiv) were added to 2.0 mL of trifluorotoluene under Ar. The resulting mixed solution was stirred at room temperature for 1 h. Then, [1,1'-binaphthyl]-2-diphenylphosphine (87.6 mg, 0.2 mmol) and ethyl acrylate (100.0 mg, 1.0 mmol) were added under argon. The resulting mixture was stirred at 150°C for 72 hours. After cooling to room temperature, the solvent was evaporated under reduced pressure. The product was separated by 300-400 mesh silica gel chromatography column with petroleum ether:ethyl acetate = 20:1 as the eluent and dried in vacuo to obtain the product with a yield of 43% and an enantiomeric excess of 93%. 1 H NMR (400 MHz, CDCl3) δ 7.93(d, J = 8.4 Hz, 1H), 7.91 – 7.86 (m, 2H), 7.83 (d, J = 8.1 Hz, 1H), 7.50 – 7.43(m, 3H), 7.33 – 7.27 (m, 4H), 7.26 – 7.21 (m, 3H), 7.20 – 7.15 (m, 1H), 7.15– 7.09 (m, 3H), 7.04 – 6.98 (m, 2H), 6.98 – 6.93 (m, 1H), 6.76 (dd, J = 8.5,0.9 Hz, 1H), 3.96 (qd, J = 7.1, 1.0 Hz, 2H), 2.63 – 2.44 (m, 2H), 2.38 – 2.20(m, 2H), 1.12 (t, J = 7.2 Hz, 3H); 13C NMR (101 MHz, CDCl3)δ 172.9, 144.1 (d, J =34.5 Hz), 137.4 (d, J = 12.7 Hz), 137.1 (d, J = 2.3 Hz), 135.4 (d, J = 11.4 Hz),135.3 (d, J = 8.6 Hz), 133.70, 133.67, 133.5 (d, J = 4.1 Hz), 133.4, 133.3 (d, J =2.3 Hz), 133.1 (d, J = 7.7 Hz), 132.0, 130.3 (d, J = 2.3 Hz), 128.4 (d, J = 5.5Hz), 128.3 (d, J = 9.1 Hz), 128.2 (d, J = 8.2 Hz), 128.04, 128.00 (d, J = 2.3 Hz),127.7, 126.9, 126.7 (d, J = 2.7 Hz), 126.6, 126.5 (d, J = 13.2 Hz), 125.4 (d, J =72.7 Hz), 60.1, 34.5, 28.8, 14.1; 31 P NMR (162 MHz, CDCl3)δ -15.02.。

Claims

1. A method for preparing a lipid chain substituted biphenyl type or phenylpyrrole type chiral monophosphine ligand, characterized in that: The steps include: Using a biphenyl or phenylpyrrole monophosphine ligand as a raw material, under the protection of an inert gas, in an organic solvent, the reaction temperature is controlled at 70-150° C., and the raw material and a fatty chain compound undergo an asymmetric carbon-hydrogen activation reaction with the participation of a chiral ligand to obtain the fatty chain-substituted biphenyl or phenylpyrrole chiral monophosphine ligand; The catalyst is monovalent iridium; The chiral ligand is selected from one of (R)-(-)-(3,5-dioxo-4-phospho-cycloheptyl[2,1-A,3,4-A']dinaphthyl)dimethylamine, N-dimethyl-[(R)-1,1'-spirodihydroindane-7,7'-diyl]phosphoramidite, (3aR,8aR)-(2,2-dimethyl-4,4,8,8-tetraphenyl-tetrahydro-[1,3]dioxazolo[4,5-e][1,3,2]dioxaphosphinylheptan-6-yl)dimethylamine or (R)-(+)-(3,5-dioxa-4-phosphocycloheptyl[2,1-a;3,4-a']dinaphthyl)-5-hydro-dibenzo[b,f]azepine; The fatty chain compound is a fatty olefin, a fatty alkyne or a derivative thereof; The structural formula of fatty olefins or their derivatives is ; The structural formula of aliphatic alkyne or its derivatives is ; R 4 independently selected from ester, alkyl or aryl groups; The raw material is selected from the compound of formula 1 or the compound of formula 11: ， ， Among them, R 1 are independently selected from substituted or unsubstituted aromatic groups; R 2 、R 3 independently selected from hydrogen, methyl, methoxy, aryl, halogen or trifluoromethyl; is a substituted or unsubstituted benzene ring, naphthalene ring, phenanthrene ring, pyrene ring, quinoline, acenaphthene, dibenzofuran ring or piperonyl ring; The structural formula of the lipid chain-substituted biphenyl or phenylpyrrole chiral monophosphine ligand is Formula 3, Formula 7 or Formula 12: ， ， 。 2. The preparation method according to claim 1, characterized in that R 4 Selected from an ester group, a C1~C5 alkyl group or an unsubstituted aryl group.

3. The preparation method according to claim 1, characterized in that The monovalent iridium is derived from one or more of (1,5-cyclooctadiene)iridium(I) chloride dimer, bis(1,5-cyclooctadiene)iridium(I) chloride dimer, bis(1,5-cyclooctadiene)-iridium trifluoromethanesulfonate, bis(1,5-cyclooctadiene)iridium(I) tetrafluoroborate or bis(ethylene)iridium chloride dimer.

4. The preparation method according to claim 1, characterized in that The molar ratio of the catalyst, chiral ligand, raw material and lipid chain compound is 5%:11%:1:5-10.

5. The preparation method according to claim 1, characterized in that The organic solvent is a mixture of one or more of toluene, trifluorotoluene, p-xylene, m-xylene, o-xylene, tetrahydrofuran or 1,4-dioxane.

6. The preparation method according to claim 1, characterized in that The inert gas is argon or nitrogen.

7. The preparation method according to claim 1, characterized in that The reaction time is 48 to 72 hours.

8. The preparation method according to claim 1, characterized in that R 1 is selected from a halogen-substituted aromatic group or an unsubstituted aromatic group.

9. The preparation method according to claim 8, characterized in that R 1 is selected from halophenyl, phenyl or thienyl.

Images