CN117024477A - Preparation method of aliphatic chain substituted biphenyl type or phenyl pyrrole type chiral monophosphine ligand - Google Patents
Preparation method of aliphatic chain substituted biphenyl type or phenyl pyrrole type chiral monophosphine ligand Download PDFInfo
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- CN117024477A CN117024477A CN202310985558.9A CN202310985558A CN117024477A CN 117024477 A CN117024477 A CN 117024477A CN 202310985558 A CN202310985558 A CN 202310985558A CN 117024477 A CN117024477 A CN 117024477A
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- 239000003446 ligand Substances 0.000 title claims abstract description 40
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 title claims abstract description 33
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical class C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 239000004305 biphenyl Substances 0.000 title claims abstract description 16
- 235000010290 biphenyl Nutrition 0.000 title claims abstract description 15
- IRTLROCMFSDSNF-UHFFFAOYSA-N 2-phenyl-1h-pyrrole Chemical compound C1=CNC(C=2C=CC=CC=2)=C1 IRTLROCMFSDSNF-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 125000001931 aliphatic group Chemical group 0.000 title claims description 9
- -1 aliphatic alkyne Chemical class 0.000 claims abstract description 59
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 7
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 5
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 5
- 239000011261 inert gas Substances 0.000 claims abstract description 5
- 230000004913 activation Effects 0.000 claims abstract description 4
- 125000004067 aliphatic alkene group Chemical group 0.000 claims abstract description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 3
- 125000003473 lipid group Chemical group 0.000 claims abstract 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 152
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 106
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 68
- 239000000203 mixture Substances 0.000 claims description 58
- 229910052786 argon Inorganic materials 0.000 claims description 53
- TVRHDFJMHSSQCP-UHFFFAOYSA-M [Ir]Cl.C1CC=CCCC=C1 Chemical class [Ir]Cl.C1CC=CCCC=C1 TVRHDFJMHSSQCP-UHFFFAOYSA-M 0.000 claims description 30
- 150000008300 phosphoramidites Chemical class 0.000 claims description 28
- YNJJJJLQPVLIEW-UHFFFAOYSA-M [Ir]Cl Chemical class [Ir]Cl YNJJJJLQPVLIEW-UHFFFAOYSA-M 0.000 claims description 26
- 150000001875 compounds Chemical class 0.000 claims description 11
- 125000003118 aryl group Chemical group 0.000 claims description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 claims description 6
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 4
- 150000001336 alkenes Chemical class 0.000 claims description 4
- 125000004185 ester group Chemical group 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 125000003944 tolyl group Chemical group 0.000 claims description 4
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 claims description 3
- XYOVOXDWRFGKEX-UHFFFAOYSA-N azepine Chemical compound N1C=CC=CC=C1 XYOVOXDWRFGKEX-UHFFFAOYSA-N 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 claims description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 150000001555 benzenes Chemical group 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 125000005059 halophenyl group Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 2
- 125000001624 naphthyl group Chemical group 0.000 claims description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical group C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 claims description 2
- 125000004591 piperonyl group Chemical group C(C1=CC=2OCOC2C=C1)* 0.000 claims description 2
- 125000005581 pyrene group Chemical group 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000007858 starting material Substances 0.000 claims description 2
- 238000006467 substitution reaction Methods 0.000 claims description 2
- 125000001544 thienyl group Chemical group 0.000 claims description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 81
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 81
- 238000003786 synthesis reaction Methods 0.000 description 57
- 230000015572 biosynthetic process Effects 0.000 description 56
- 239000002904 solvent Substances 0.000 description 56
- 238000003756 stirring Methods 0.000 description 56
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 55
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 55
- 239000003208 petroleum Substances 0.000 description 55
- 238000001291 vacuum drying Methods 0.000 description 55
- 239000011259 mixed solution Substances 0.000 description 53
- XNMQEEKYCVKGBD-UHFFFAOYSA-N 2-butyne Chemical compound CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 description 47
- 238000010898 silica gel chromatography Methods 0.000 description 43
- 238000010828 elution Methods 0.000 description 27
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 24
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 24
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 24
- VYXHVRARDIDEHS-UHFFFAOYSA-N 1,5-cyclooctadiene Chemical compound C1CC=CCCC=C1 VYXHVRARDIDEHS-UHFFFAOYSA-N 0.000 description 21
- 239000004912 1,5-cyclooctadiene Substances 0.000 description 21
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 239000000741 silica gel Substances 0.000 description 12
- 229910002027 silica gel Inorganic materials 0.000 description 12
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 9
- RNXMVQFMHXXZLO-UHFFFAOYSA-N (2-naphthalen-1-ylphenyl)-diphenylphosphane Chemical compound C1=CC=CC=C1P(C=1C(=CC=CC=1)C=1C2=CC=CC=C2C=CC=1)C1=CC=CC=C1 RNXMVQFMHXXZLO-UHFFFAOYSA-N 0.000 description 8
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 7
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 4
- 125000005605 benzo group Chemical group 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- JAZCEXBNIYKZDI-UHFFFAOYSA-N [Ir+] Chemical compound [Ir+] JAZCEXBNIYKZDI-UHFFFAOYSA-N 0.000 description 3
- 150000002632 lipids Chemical group 0.000 description 3
- RYSSNRHEVRMTJP-UHFFFAOYSA-N (2-phenanthren-9-ylphenyl)-diphenylphosphane Chemical compound C1=CC=CC=C1P(C=1C(=CC=CC=1)C=1C2=CC=CC=C2C2=CC=CC=C2C=1)C1=CC=CC=C1 RYSSNRHEVRMTJP-UHFFFAOYSA-N 0.000 description 2
- CFPMTYLOUSWLLM-UHFFFAOYSA-N 1-naphthalen-2-ylnaphthalene Chemical group C1=CC=C2C(C3=CC4=CC=CC=C4C=C3)=CC=CC2=C1 CFPMTYLOUSWLLM-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- ZDZHCHYQNPQSGG-UHFFFAOYSA-N binaphthyl group Chemical group C1(=CC=CC2=CC=CC=C12)C1=CC=CC2=CC=CC=C12 ZDZHCHYQNPQSGG-UHFFFAOYSA-N 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000006880 cross-coupling reaction Methods 0.000 description 2
- UZVGSSNIUNSOFA-UHFFFAOYSA-N dibenzofuran-1-carboxylic acid Chemical compound O1C2=CC=CC=C2C2=C1C=CC=C2C(=O)O UZVGSSNIUNSOFA-UHFFFAOYSA-N 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- VBHXIMACZBQHPX-UHFFFAOYSA-N 2,2,2-trifluoroethyl prop-2-enoate Chemical compound FC(F)(F)COC(=O)C=C VBHXIMACZBQHPX-UHFFFAOYSA-N 0.000 description 1
- RCFYJIGZQAOTFV-UHFFFAOYSA-N 2,9-dimethyldec-5-yne Chemical compound CC(C)CCC#CCCC(C)C RCFYJIGZQAOTFV-UHFFFAOYSA-N 0.000 description 1
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 description 1
- JHUUPUMBZGWODW-UHFFFAOYSA-N 3,6-dihydro-1,2-dioxine Chemical compound C1OOCC=C1 JHUUPUMBZGWODW-UHFFFAOYSA-N 0.000 description 1
- DQQNMIPXXNPGCV-UHFFFAOYSA-N 3-hexyne Chemical compound CCC#CCC DQQNMIPXXNPGCV-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 238000006069 Suzuki reaction reaction Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 238000005937 allylation reaction Methods 0.000 description 1
- 238000007294 asymmetric addition reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000005347 biaryls Chemical group 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- VIGVRXYWWFPORY-UHFFFAOYSA-N diphenylborinic acid Chemical compound C=1C=CC=CC=1B(O)C1=CC=CC=C1 VIGVRXYWWFPORY-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 229940078552 o-xylene Drugs 0.000 description 1
- GZTNBKQTTZSQNS-UHFFFAOYSA-N oct-4-yne Chemical compound CCCC#CCCC GZTNBKQTTZSQNS-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- GHUURDQYRGVEHX-UHFFFAOYSA-N prop-1-ynylbenzene Chemical compound CC#CC1=CC=CC=C1 GHUURDQYRGVEHX-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 125000004205 trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 1
- 238000010977 unit operation Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/5022—Aromatic phosphines (P-C aromatic linkage)
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B53/00—Asymmetric syntheses
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
- C07F9/572—Five-membered rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
- C07F9/576—Six-membered rings
- C07F9/60—Quinoline or hydrogenated quinoline ring systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/655—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms
- C07F9/65515—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms the oxygen atom being part of a five-membered ring
- C07F9/65517—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms the oxygen atom being part of a five-membered ring condensed with carbocyclic rings or carbocyclic ring systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having sulfur atoms, with or without selenium or tellurium atoms, as the only ring hetero atoms
- C07F9/655345—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having sulfur atoms, with or without selenium or tellurium atoms, as the only ring hetero atoms the sulfur atom being part of a five-membered ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/07—Optical isomers
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- Life Sciences & Earth Sciences (AREA)
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Abstract
The invention discloses a preparation method of a lipid chain substituted biphenyl or phenyl pyrrole chiral monophosphine ligand, which comprises the following steps: the method is characterized in that biphenyl or phenyl pyrrole type monophosphine ligand is used as a raw material, the reaction temperature is controlled to be 70-150 ℃ in an organic solution under the protection of inert gas, and the raw material and aliphatic alkene, aliphatic alkyne or derivatives thereof are subjected to asymmetric hydrocarbon activation reaction under the participation of chiral ligand through catalysis of monovalent iridium catalyst. The synthetic route is not reported in the literature, and the raw materials are cheap and easy to obtain; the unit is simple to operate, has low equipment requirement, and is suitable for quickly constructing a novel chiral monophosphine ligand library.
Description
Technical Field
The invention belongs to the field of organic synthesis, and particularly relates to a preparation method of a lipid chain substituted biphenyl type or phenyl pyrrole type chiral monophosphine ligand.
Background
Asymmetric transition metal catalytic reactions are closely related to the development of chiral ligands, and chiral phosphine ligands are also becoming more and more important to synthetic chemists as the most widely used ligands in the increasingly popular cross-coupling field. MOP-type ligands of the biaryl or binaphthyl type, among which the axial chirality is present, have been studied for use in asymmetric transition metal catalyzed reactions, such as olefin, ketocarbonyl asymmetric addition reactions, and have achieved excellent results. However, the synthesis of the chiral phosphine ligand is long (the first step of synthesizing diphenyl boric acid, the second step of Suzuki reaction, the third step of cross coupling reaction for preparing the phosphine ligand, and the fourth step of chiral resolution), so that the problems of single structure, low total yield and the like are caused by larger restriction of substituent groups. These problems greatly affect the development and application of such ligands.
Disclosure of Invention
Aiming at the problems, the invention provides a preparation method of a novel aliphatic chain substituted biphenyl or phenyl pyrrole chiral monophosphine ligand, which has the advantages of simple steps, high yield, high chemical selectivity and high stereoselectivity, and is suitable for rapidly preparing the chiral monophosphine ligand of the type by only one step.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a method for preparing a biphenyl or phenyl pyrrole chiral monophosphine ligand with a lipid chain substitution, which comprises the following steps:
taking biphenyl type or phenyl pyrrole type monophosphine ligand as a raw material, controlling the reaction temperature to be 70-150 ℃ in an organic solution under the protection of inert gas, and carrying out asymmetric hydrocarbon activation reaction on the raw material and a lipid chain compound under the participation of chiral ligand by catalyst to obtain the lipid chain substituted biphenyl type or phenyl pyrrole type chiral monophosphine ligand;
the catalyst is monovalent iridium;
the aliphatic chain compound is aliphatic alkene, aliphatic alkyne or derivatives thereof;
the fatty olefin or its derivative has the structural formula；
The structural formula of the aliphatic alkyne or the derivative thereof is；
R 4 Independently selected from ester groups, alkyl groups or aryl groups.
Preferably, R 4 Selected from ester groups, C1-C5 alkyl groups or unsubstituted aryl groups.
Preferably, the monovalent iridium is one or more selected from (1, 5-cyclooctadiene) iridium (I) chloride dimer, bicyclo-octene iridium (I) chloride dimer, bis (1, 5-cyclooctadiene) -iridium triflate, bis (1, 5-cyclooctadiene) iridium tetrafluoroborate (I) or bis (ethylene) iridium chloride dimer; preferably, the monovalent iridium is derived from (1, 5-cyclooctadiene) chloroiridium (I) dimer.
Preferably, the molar ratio of the catalyst, the chiral ligand, the raw material and the aliphatic chain compound is 5 percent to 11 percent to 1:5-10.
Preferably, the organic solvent is toluene, benzotrifluoride, paraxylene, metaxylene, orthoxylene, tetrahydrofuran or a mixture of one or more of 1, 4-dioxane; the preferred organic solvent is toluene.
Preferably, 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' -spiroindan-7, 7 '-diyl ] phosphoramidite, (3 aR,8 aR) - (2, 2-dimethyl-4,4,8,8-tetraphenyl-tetrahydro- [1,3] dioxa [4,5-e ] [1,3,2] dioxa-zepin-6-yl) dimethylamine or (R) - (+) - (3, 5-dioxa-4-phospho-cyclohepta [2,1-a;3,4-a' ] dinaphthyl-4-yl) -5 hydrogen-dibenzo [ b, f ] azepine; a preferred chiral ligand is (R) - (-) - (3, 5-dioxo-4-phospho-cycloheptyl [2,1-A,3,4-A' ] dinaphthyl) dimethylamine.
Preferably, the inert gas is argon or nitrogen.
Preferably, the reaction time is 48-72 h.
Preferably, the starting material is selected from the group consisting of compounds of formula 1 or 11:
，/>，
wherein R is 1 Independently selected from substituted or unsubstituted aryl; r is R 2 、R 3 Independently selected from a hydrogen atom, 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.
Preferably, R 1 Selected from halogen substituted aryl or unsubstituted aryl. More preferably, R 1 Selected from halophenyl, phenyl, or thienyl.
The structures of the products of the reaction of the compound of the formula 1 and the fatty alkene or the derivative thereof and the products of the reaction of the compound of the formula 1 and the fatty alkyne or the derivative thereof are respectively shown as formulas 3 and 7:，/>。
when the compound of formula 1 is a binaphthyl-type monophosphine ligand, it may be a 1,1' -binaphthyl-type monophosphine ligand or a 1, 2-binaphthyl-type monophosphine ligand.
The structure of the product of the reaction of a compound of formula 11 with an aliphatic alkyne or derivative thereof is shown in formula 12:
。
the partial chemical reaction equation of the preparation method is as follows:
，
wherein R is 1 、R 2 、R 3 、R 4 Is as defined above. L (L) * Is chiral ligand.
The invention has the beneficial effects that:
In the prior art, the reaction catalyzed by iridium (I) and chiral ligand phosphine can only realize asymmetric nucleophilic allylation type reaction, and the reaction generally needs to be realized by introducing a relatively active leaving group into a reaction substrate. The invention researches on the reaction of activating hydrocarbon bonds which is richer and more inert in organic compounds, creatively adopts a catalytic system of iridium (I) and chiral ligand phosphine ligand to realize the hydrocarbon bond activation reaction with higher difficulty, and successfully prepares the aliphatic chain substituted biphenyl type or phenyl pyrrole type chiral phosphine ligand.
The invention provides a synthetic route of a biphenyl or phenyl pyrrole chiral monophosphine ligand with a substituted aliphatic chain, raw materials are cheap and easy to obtain, unit operation is simple, equipment requirements are low, and the method is suitable for quickly constructing a novel monophosphine ligand library.
Additional aspects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Detailed Description
The following is a specific embodiment of the present invention, and the technical solution of the present invention is further described, but the present invention is not limited to this embodiment.
EXAMPLE 1 Synthesis of (R, E) - (2- (2- (but-2-en-2-yl) naphthalen-1-yl) phenyl) diphenylphosphine
25 In a mL Schlenk tube, 1, 5-cyclooctadiene) iridium (I) chloride dimer (3.4 mg,0.01 mmol,0.05 eq) and (R) -N-dimethyl- [ (S) -1,1 '-spiroindan-7, 7' -diyl were added to 2.0mL toluene under Ar in a 25.0mL dry Schlenk tube with stirring bar]Phosphoramidite (7.3 mg,0.022 mmol,0.11 eq). The resulting mixed solution was stirred at room temperature for 1h. (2- (naphthalen-1-yl) phenyl) diphenylphosphine (77.6 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℃or 90℃for 72 hours, cooled to room temperature, the solvent was distilled off under reduced pressure, and separated by a 300-400 mesh silica gel column chromatography, petroleum ether: two (II)Methyl chloride=10:1, and the product is obtained after vacuum drying, the yield is 82%, and the enantiomer excess value is 97%. 1 H NMR (400 MHz, CDCl 3 )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 (101 MHz, CDCl 3 )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= 18.2 Hz), 131.92, 131.85 (d, J = 6.4 Hz), 128.3 (d,J= 17.3 Hz), 128.1 (d,J= 5.4 Hz), 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, CDCl 3 )δ -15.66.
Example 2 Synthesis of (R, E) - (2- (2- (but-2-en-2-yl) naphthalen-1-yl) -4-methylphenyl) diphenylphosphine
25 In a mL Schlenk tube, in a 25.0mL dry Schlenk tube with stirring bar, (1, 5-cyclooctadiene) iridium (I) chloride dimer (3.4 mg,0.01 mmol,0.05 eq) and (R) are added to 2.0mL toluene under ArN-dimethyl- [ (S) -1,1 '-spiroindan-7, 7' -diyl]Phosphoramidite (7.3 mg,0.022 mmol,0.11 eq). The resulting mixed solution was stirred at room temperature for 1h. (4-methyl-2- (naphthalen-1-yl) phenyl) diphenylphosphine (80.4 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℃or 90℃for 72 hours, cooled to room temperature, the solvent was distilled off under reduced pressure, and separated by 300-400 mesh silica gel column chromatography, petroleum ether: dichloromethane=10:1 elution, and vacuum drying to obtain the product with yield of 78% and enantiomer excess value of 97%. 1 H NMR (500 MHz, CDCl 3 )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, CDCl 3 )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= 17.8 Hz), 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, CDCl 3 )δ -16.80.
EXAMPLE 3 Synthesis of (R, E) - (2- (2- (but-2-en-2-yl) naphthalen-1-yl) -5-methylphenyl) diphenylphosphine
25 In a mL Schlenk tube, in a 25.0mL dry Schlenk tube with stirring bar, (1, 5-cyclooctadiene) iridium (I) chloride dimer (3.4 mg,0.01 mmol,0.05 eq) and (R) are added to 2.0mL toluene under ArN-dimethyl- [ (S) -1,1 '-spiroindan-7, 7' -diyl]Phosphoramidite (7.3 mg,0.022 mmol,0.11 eq). The resulting mixed solution was stirred at room temperature for 1h. (5-methyl-2- (naphthalen-1-yl) phenyl) diphenylphosphine (80.4 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℃for 72 hours, cooled to room temperature and the solvent was distilled off under reduced pressure, separated by a 300-400 mesh silica gel column chromatography, petroleum ether: dichloromethane=10:1 elution, and vacuum drying to obtain the product with yield of 90% and enantiomer excess value of 99%. 1 H NMR (400 MHz, CDCl 3 ) δ 7.81 (d,J= 8.4 Hz, 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); 13 C NMR (101 MHz, CDCl 3 )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, CDCl 3 )δ -16.80.
EXAMPLE 4 Synthesis of (R, E) - (2- (2- (but-2-en-2-yl) -4-methylnaphthalen-1-yl) phenyl) diphenylphosphine
25 In a mL Schlenk tube, in a 25.0mL dry Schlenk tube with stirring bar, (1, 5-cyclooctadiene) iridium (I) chloride dimer (3.4 mg,0.01 mmol,0.05 eq) and (R) are added to 2.0mL toluene under Ar N-dimethyl- [ (S) -1,1 '-spiroindan-7, 7' -diyl]Phosphoramidite (7.3 mg,0.022 mmol,0.11 eq). The resulting mixed solution was stirred at room temperature for 1h. (2- (4-methylnaphthalen-1-yl) phenyl) diphenylphosphine (80.4 mg,0.2 mmol) and 2-butyne (108.0 mg,2.0 mmol) were then added under argon, the resulting mixture was stirred at 70 ℃ for 72 hours, cooled to room temperature, the solvent was distilled off under reduced pressure, separated by 300-400 mesh silica gel chromatography column, petroleum ether: dichloromethane=10:1 elution, and vacuum drying to obtain the product with yield of 78% and enantiomer excess value of 99%. 1 H NMR (500 MHz, CDCl 3 )δ 8.01 (d,J= 8.4 Hz, 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, CDCl 3 )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, CDCl 3 )δ -15.99.
Example 5 Synthesis of (R, E) - (2- (2- (but-2-en-2-yl) naphthalen-1-yl) -4, 5-dimethylphenyl) diphenylphosphine
25 In a mL Schlenk tube, in a 25.0mL dry Schlenk tube with stirring bar, (1, 5-cyclooctadiene) iridium (I) chloride dimer (3.4 mg,0.01 mmol,0.05 eq) and (R) are added to 2.0mL toluene under ArN-dimethyl- [ (S) -1,1 '-spiroindan-7, 7' -diyl]Phosphoramidite (7.3 mg,0.022 mmol,0.11 eq). The resulting mixed solution was stirred at room temperature for 1h. (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 then added under argon, the resulting mixture was stirred at 70℃for 72 hours, cooled to room temperature and the solvent was distilled off under reduced pressure, separated by a 300-400 mesh silica gel column, petroleum ether: dichloromethane=10:1 elution, and vacuum drying to obtain the product with yield of 62% and enantiomer excess value of 97%. 1 H NMR (400 MHz, CDCl 3 )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, CDCl 3 )δ 144.1 (d,J= 35.9 Hz), 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= 2.5 Hz), 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= 1.8 Hz), 13.8; 31 P NMR (162 MHz, CDCl 3 )δ -16.69.
EXAMPLE 6 Synthesis of (R, E) - (2- (2- (but-2-en-2-yl) -4-phenylnaphthalen-1-yl) phenyl) diphenylphosphine
25 In a mL Schlenk tube, in a 25.0mL dry Schlenk tube with stirring bar, (1, 5-cyclooctadiene) iridium (I) chloride dimer (3.4 mg,0.01 mmol,0.05 eq) and (R) are added to 2.0mL toluene under ArN-dimethyl- [ (S) -1,1 '-spiroindan-7, 7' -diyl]Phosphoramidite (7.3 mg,0.022 mmol,0.11 eq). The resulting mixed solution was stirred at room temperature for 1h. Diphenyl (2- (4-phenylnaphthalen-1-yl) phenyl) phosphine (92.8 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 ℃ for 72 hours, cooled to room temperature, the solvent was distilled off under reduced pressure, and separated by 300-400 mesh silica gel chromatography column, petroleum ether: dichloromethane=10:1 elution, and vacuum drying to obtain the product with yield of 68% and enantiomer excess value of 98%. 1 H NMR (500 MHz, CDCl 3 )δ 7.95 (d,J= 8.2 Hz, 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, 1.5 Hz, 1H), 1.68 (s, 3H), 1.48 (d,J= 6.8 Hz, 3H); 13 C NMR (126 MHz, CDCl 3 )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= 18.5 Hz), 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, CDCl 3 )δ -15.52.
EXAMPLE 7 Synthesis of (R, E) - (2- (2- (but-2-en-2-yl) naphthalen-1-yl) -4-methoxyphenyl) diphenylphosphine
25 In a mL Schlenk tube, in a 25.0mL dry Schlenk tube with stirring bar, (1, 5-cyclooctadiene) iridium (I) chloride dimer (3.4 mg,0.01 mmol,0.05 eq) and (R) are added to 2.0mL toluene under Ar N-dimethyl- [ (S) -1,1 '-spiroindan-7, 7' -diyl]Phosphoramidite (7.3 mg,0.022 mmol,0.11 eq). The resulting mixed solution was stirred at room temperature for 1h. (4-methoxy-2- (naphthalen-1-yl) phenyl) diphenylphosphine (83.6 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℃for 72 hours, cooled to room temperature, the solvent was distilled off under reduced pressure, and separated by a 300-400 mesh silica gel column, petroleum ether: dichloromethane=10:1 elution, and vacuum drying to obtain the product with 76% yield and 94% enantiomer excess. 1 H NMR (400 MHz, CDCl 3 )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, CDCl 3 )δ 159.7, 148.2 (d,J= 37.2 Hz), 142.1 (d,J= 2.3 Hz), 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, CDCl 3 )δ -17.81.
EXAMPLE 8 Synthesis of (R, E) - (2- (2- (but-2-en-2-yl) -4-methoxynaphthalen-1-yl) phenyl) diphenylphosphine
25 In a mL Schlenk tube, in a 25.0mL dry Schlenk tube with stirring bar, (1, 5-cyclooctadiene) iridium (I) chloride dimer (3.4 mg,0.01 mmol,0.05 eq) and (R) are added to 2.0mL toluene under ArN-dimethyl- [ (S) -1,1 '-spiroindan-7, 7' -diyl]Phosphoramidite (7.3 mg,0.022 mmol,0.11 eq). The resulting mixed solution was stirred at room temperature for 1h. (2- (4-methoxynaphthalen-1-yl) phenyl) diphenylphosphine (83.6 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℃for 72 hours, cooled to room temperature, the solvent was distilled off under reduced pressure, and separated by a 300-400 mesh silica gel column chromatography, petroleum ether: dichloromethane=10:1 elution, and vacuum drying to obtain the product with 71% yield and 99% enantiomer excess. 1 H NMR (500 MHz, CDCl 3 )δ 8.29 (d,J= 8.3 Hz, 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, CDCl 3 )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= 4.0 Hz), 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= 1.7 Hz); 31 P NMR (202 MHz, CDCl 3 )δ -15.76.
EXAMPLE 9 Synthesis of (R, E) - (6- (2- (but-2-en-2-yl) naphthalen-1-yl) benzo [ d ] [1,3] dioxo-5-yl) diphenylphosphine
25 In a mL Schlenk tube, in a 25.0mL dry Schlenk tube with stirring bar, 2.0mL toluene was added (1, 5-cyclooctadiene under Ar) Iridium (I) chloride dimer (3.4 mg,0.01 mmol,0.05 eq) and (R) -N-dimethyl- [ (S) -1,1 '-spiroindan-7, 7' -diyl]Phosphoramidite (7.3 mg,0.022 mmol,0.11 eq). The resulting mixed solution was stirred at room temperature for 1h. (6- (naphthalen-1-yl) benzo [ d ] is then added under argon][1,3]Dihydroxy-5-yl) diphenylphosphine (86.2 mg,0.2 mmol) and butyne 2 (54.0 mg,1.0 mmol), the resulting mixture was stirred at 70℃for 72 hours, cooled to room temperature, the solvent was distilled off under reduced pressure, and separated by a 300-400 mesh silica gel column chromatography, petroleum ether: dichloromethane=10:1 elution, and vacuum drying to obtain the product with yield of 78% and enantiomer excess value of 95%. 1 H NMR (400 MHz, CDCl 3 )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= 3.7 Hz, 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, CDCl 3 )δ 148.2, 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, CDCl 3 )δ -15.41.
EXAMPLE 10 Synthesis of (R, E) - (2- (2- (but-2-en-2-yl) naphthalen-1-yl) -5-fluorophenyl) diphenylphosphine
25 In a mL Schlenk tube, in a 25.0mL dry Schlenk tube with stirring bar, (1, 5-cyclooctadiene) iridium (I) chloride dimer (3.4 mg,0.01 mmol,0.05 eq) and (R) are added to 2.0mL toluene under Ar N-dimethyl- [ (S) -1,1 '-spiroindan-7, 7' -diyl]Phosphoramidite (7.3 mg,0.022 mmol,0.11 eq). The formed mixed solution is added inStirring was carried out at room temperature for 1h. (5-fluoro-2- (naphthalen-1-yl) phenyl) diphenylphosphine (80.4 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℃for 72 hours, cooled to room temperature and the solvent was distilled off under reduced pressure, separated by a 300-400 mesh silica gel column chromatography, petroleum ether: dichloromethane=10:1 elution, and vacuum drying to obtain the product with yield of 78% and enantiomer excess value of 99%. 1 H NMR (400 MHz, CDCl 3 )δ 7.82 (d,J= 8.4 Hz, 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= 21.3 Hz), 133.3 (t,J= 6.8 Hz), 132.8 (d,J= 18.6 Hz), 131.9, 128.6, 128.3 (d,J= 5.9 Hz), 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, CDCl 3 )δ -15.01; 19 F NMR (376 MHz, CDCl 3 )δ -114.59.
EXAMPLE 11 Synthesis of (R, E) - (2- (2- (but-2-en-2-yl) naphthalen-1-yl) -4, 5-difluorophenyl) diphenylphosphine
25 In a mL Schlenk tube, in a 25.0mL dry Schlenk tube with stirring bar, (1, 5-cyclooctadiene) iridium (I) chloride dimer (3.4 mg,0.01 mmol,0.05 eq) and (R) are added to 2.0mL toluene under ArN-dimethyl- [ (S) -1,1 '-spiroindan-7, 7' -diyl]Phosphoramidite (7.3 mg,0.022 mmol,0.11 eq). The resulting mixed solution was stirred at room temperature for 1h. (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 then added under argon and the resulting mixture was admixed The compound is stirred for 72 hours at 120 ℃, cooled to room temperature, the solvent is distilled off under reduced pressure, and separated by a 300-400 mesh silica gel chromatographic column, petroleum ether: dichloromethane=10:1 elution, and vacuum drying to obtain the product with yield of 57% and enantiomer excess value of 97%. 1 H NMR (500 MHz, CDCl 3 )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 P NMR (202 MHz, CDCl 3 )δ -16.29; 19 F NMR (471 MHz, CDCl 3 )δ -137.10 (d,J= 21.7 Hz, 1F), -138.76 (d,J= 21.7 Hz, 1F).
EXAMPLE 12 Synthesis of (R, E) - (2- (2- (but-2-en-2-yl) naphthalen-1-yl) -4-chlorophenyl) diphenylphosphine
25 In a mL Schlenk tube, in a 25.0mL dry Schlenk tube with stirring bar, at N 2 To 2.0ml of toluene were added (1, 5-cyclooctadiene) iridium (I) chloride dimer (3.4 mg,0.01 mmol,0.05 equivalent) and (R) a-N-dimethyl- [ (S) -1,1 '-spiroindan-7, 7' -diyl]Phosphoramidite (7.3 mg,0.022 mmol,0.11 eq). The resulting mixed solution was stirred at room temperature for 1h. (4-chloro-2- (naphthalen-1-yl) phenyl) diphenylphosphine (84.4 mg,0.2 mmol) and 2-butyne (54.0 mg,1.0 mmol) were then added under nitrogen and the resulting mixture stirred at 150 ℃After 48 hours, cooling to room temperature, decompressing and evaporating the solvent, separating by a 300-400 mesh silica gel chromatographic column, and petroleum ether: dichloromethane=10:1 elution, and vacuum drying to obtain the product with the yield of 65% and the enantiomer excess value of 97%. 1 H NMR (400 MHz, CDCl 3 )δ 7.83 (d,J= 8.3 Hz, 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= 2.3 Hz), 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, CDCl 3 )δ -17.55.
EXAMPLE 13 Synthesis of (R, E) - (2- (2- (but-2-en-2-yl) -4-chloronaphthalen-1-yl) phenyl) diphenylphosphine
25 In a mL Schlenk tube, in a 25.0mL dry Schlenk tube with stirring bar, (1, 5-cyclooctadiene) iridium (I) chloride dimer (3.4 mg,0.01 mmol,0.05 eq) and (R) are added to 2.0mL toluene under ArN-dimethyl- [ (S) -1,1 '-spiroindan-7, 7' -diyl]Phosphoramidite (7.3 mg,0.022 mmol,0.11 eq). The resulting mixed solution was stirred at room temperature for 1h. (2- (4-chloronaphthalen-1-yl) phenyl) diphenylphosphine (84.4 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℃for 72 hours, cooled to room temperature, the solvent was distilled off under reduced pressure, and separated by 300-400 mesh silica gel chromatography column, petroleum ether: dichloromethane=10:1 elution, and vacuum drying to obtain the product with yield of 87% and enantiomer excess value of 97%. 1 H NMR (500 MHz, CDCl 3 )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, CDCl 3 )δ 145.5 (d,J= 34.8 Hz), 142.5 (d,J= 1.7 Hz), 138.05, 138.04 (d, J = 24.3 Hz), 137.6 (d,J= 13.3 Hz), 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, CDCl 3 )δ -15.72.
EXAMPLE 14 Synthesis of (R, E) - (2- (2- (but-2-en-2-yl) naphthalen-1-yl) -4- (trifluoromethyl) phenyl) diphenylphosphine
25 In a mL Schlenk tube, in a 25.0mL dry Schlenk tube with stirring bar, (1, 5-cyclooctadiene) iridium (I) chloride dimer (3.4 mg,0.01 mmol,0.05 eq) and (R) are added to 2.0mL toluene under ArN-dimethyl- [ (S) -1,1 '-spiroindan-7, 7' -diyl]Phosphoramidite (7.3 mg,0.022 mmol,0.11 eq). The resulting mixed solution was stirred at room temperature for 1h. (2- (naphthalen-1-yl) -4- (trifluoromethyl) phenyl) diphenylphosphine (91.2 mg,0.2 mmol) and 2-butyne (54.0 mg,1.0 mmol) were then added under argon and the resulting mixture stirred at 70℃for 72 hours, cooled to room temperature and the solvent was distilled off under reduced pressure and separated by a 300-400 mesh silica gel column, petroleum ether: dichloromethane=10:1 elution, and vacuum drying to obtain the product with a yield of 51% and an enantiomer excess value of 98%. 1 H NMR (500 MHz, CDCl 3 )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= 7.4 Hz, 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= 6.8 Hz, 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= 21.4 Hz), 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, CDCl 3 )δ -15.87; 19 F NMR (471 MHz, CDCl 3 )δ -62.65.
EXAMPLE 15 Synthesis of (R, E) - (2- (2- (but-2-en-2-yl) naphthalen-1-yl) -5- (trifluoromethyl) phenyl) diphenylphosphine
25 In a mL Schlenk tube, 1, 5-cyclooctadiene) iridium (I) chloride dimer (3.4 mg,0.01 mmol,0.05 eq) and (R) - (+) - (3, 5-dioxa-4-phosphocyclohepta [2,1-a;3,4-a ') were added to 2.0mL toluene under Ar in a 25.0mL dry Schlenk tube with stirring bar']Dinaphthyl-4-yl) -5-hydro-dibenzo [ b, f]Azepine (7.3 mg,0.022 mmol,0.11 eq). The resulting mixed solution was stirred at room temperature for 1h. (2- (naphthalen-1-yl) -5- (trifluoromethyl) phenyl) diphenylphosphine (91.2 mg,0.2 mmol) and 2-butyne (54.0 mg,1.0 mmol) were then added under argon and the resulting mixture stirred at 70℃for 72 hours, cooled to room temperature and the solvent was distilled off under reduced pressure and separated by a 300-400 mesh silica gel column, petroleum ether: dichloromethane=10:1 elution, and vacuum drying to obtain the product with 73% yield and 95% enantiomer excess. 1 H NMR (500 MHz, CDCl 3 )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= 5.2 Hz), 131.9, 131.3 (t,J= 3.2 Hz), 129.5 (q,J= 32.1 Hz), 128.7, 128.4 (d,J= 5.2 Hz), 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; 31 P NMR (202 MHz, CDCl 3 )δ -15.40; 19 F NMR (471 MHz, CDCl 3 )δ -62.30.
EXAMPLE 16 Synthesis of (R, E) - (2- (4- (but-2-en-2-yl) -1, 2-dihydroacenaphthylen-5-yl) phenyl) diphenylphosphine
25 In a mL Schlenk tube, in a 25.0mL dry Schlenk tube with stirring bar, (1, 5-cyclooctadiene) iridium (I) chloride dimer (3.4 mg,0.01 mmol,0.05 eq) and (R) are added to 2.0mL toluene under Ar N-dimethyl- [ (S) -1,1 '-spiroindan-7, 7' -diyl]Phosphoramidite (7.3 mg,0.022 mmol,0.11 eq). The resulting mixed solution was stirred at room temperature for 1h. (2- (1, 2-Acenaphthylen-5-yl) phenyl) diphenylphosphine (91.2 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℃for 72 hours, cooled to room temperature, the solvent was distilled off under reduced pressure, and separated by a 300-400 mesh silica gel column, petroleum ether: dichloromethane=10:1 elution, and vacuum drying to obtain the product with 76% yield and 97% enantiomer excess. 1 H NMR (500 MHz, CDCl 3 )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= 8.2 Hz, 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= 20.8 Hz), 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= 2.3 Hz), 121.8, 120.6, 118.5, 30.5, 30.2, 17.9, 13.8; 31 P NMR (202 MHz, CDCl 3 )δ -16.06.
EXAMPLE 17 Synthesis of (S, E) - (2- (10- (but-2-en-2-yl) phenanthren-9-yl) phenyl) diphenylphosphine
25 In a mL Schlenk tube, in a 25.0mL dry Schlenk tube with stirring bar, (1, 5-cyclooctadiene) iridium (I) chloride dimer (3.4 mg,0.01 mmol,0.05 eq) and (R) are added to 2.0mL toluene under ArN-dimethyl- [ (S) -1,1 '-spiroindan-7, 7' -diyl]Phosphoramidite (7.3 mg,0.022 mmol,0.11 eq). The resulting mixed solution was stirred at room temperature for 1h. (2- (phenanthren-9-yl) phenyl) diphenylphosphine (87.6 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℃for 72 hours, cooled to room temperature, the solvent was distilled off under reduced pressure, separated by a 300-400 mesh silica gel column chromatography, petroleum ether: dichloromethane=10:1 elution, and vacuum drying to obtain the product with yield of 43% and enantiomer excess value of 97%. 1 H NMR (500 MHz, CDCl 3 )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, CDCl 3 )δ 146.7 (d,J= 34.7 Hz), 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, CDCl 3 )δ -15.50.
EXAMPLE 18 Synthesis of (R, E) - (2- (2- (but-2-en-2-yl) pyren-1-yl) phenyl) diphenylphosphine
25 In a mL Schlenk tube, in a 25.0mL dry Schlenk tube with stirring bar, (1, 5-cyclooctadiene) iridium (I) chloride dimer (3.4 mg,0.01 mmol,0.05 eq) and (3 aR,8 aR) - (2, 2-dimethyl-4,4,8,8-tetraphenyl-tetrahydro- [1, 3) were added to 2.0mL toluene under Ar]Dioxazolo [4,5-e ]][1,3,2]Dioxaphosphepin-6-yl) dimethylamine (7.3 mg,0.022 mmol,0.11 eq). The resulting mixed solution was stirred at room temperature for 1h. Diphenyl (2- (pyren-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 ℃ for 72 hours, cooled to room temperature, the solvent was distilled off under reduced pressure, separated by 300-400 mesh silica gel chromatography column, petroleum ether: dichloromethane=10:1 elution, and vacuum drying to obtain the product with yield of 59% and enantiomer excess value of 99%. 1 H NMR (500 MHz, CDCl 3 )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, 1.5 Hz, 1H), 1.83 (s, 3H), 1.64 (dd, J = 6.8, 1.3 Hz, 3H).; 13 C NMR (101 MHz, CDCl 3 )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= 5.9 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= 6.4 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= 15.9 Hz), 124.6, 123.3, 18.2, 14.0; 31 P NMR (202 MHz, CDCl 3 )δ -15.42.
EXAMPLE 19 Synthesis of (R, E) - (2- (but-2-en-2-yl) - [1,2 '-binaphthyl ] -3' -yl) diphenylphosphine
25 In a mL Schlenk tube, bicycloocteneiridium (I) chloride dimer (3.4 mg,0.01 mmol,0.05 eq) and (R) are added to 2.0mL toluene under Ar in a 25.0mL dry Schlenk tube with stirring bar N-dimethyl- [ (S) -1,1 '-spiroindan-7, 7' -diyl]Phosphoramidite (7.3 mg,0.022 mmol,0.11 eq). The resulting mixed solution was stirred at room temperature for 1h. Then adding [1,2' -binaphthyl ] under argon]-3' -diphenylphosphine (87.6 mg,0.2 mmol) and 2-butyne (54.0 mg,1.0 mmol), the resulting mixture was stirred at 70 ℃ for 72 hours, cooled to room temperature, the solvent was distilled off under reduced pressure, and separated by a 300-400 mesh silica gel column chromatography, petroleum ether: dichloromethane=10:1 elution, and vacuum drying to obtain the product with yield of 74% and enantiomer excess value of 99%. 1 H NMR (500 MHz, CDCl 3 )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, 1.5 Hz, 1H), 1.83 (s, 3H), 1.64 (dd, J = 6.8, 1.3 Hz, 3H).; 13 C NMR (101 MHz, CDCl 3 )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= 5.9 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= 6.4 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= 15.9 Hz), 124.6, 123.3, 18.2, 14.0; 31 P NMR (202 MHz, CDCl 3 )δ -15.42.
EXAMPLE 20 Synthesis of (S, E) -3- (but-2-en-2-yl) -4- (2- (diphenylphosphino) phenyl) quinoline
25 In a mL Schlenk tube, in a 25.0mL dry Schlenk tube with stirring bar, (1, 5-cyclooctadiene) iridium (I) chloride dimer (3.4 mg,0.01 mmol,0.05 eq) and (R) are added to 2.0mL toluene under ArN-dimethyl- [ (S) -1,1 '-spiroindan-7, 7' -diyl]Phosphoramidite (7.3 mg,0.022 mmol,0.11 eq). The resulting mixed solution was stirred at room temperature for 1h. 4- (2- (diphenylphosphino) phenyl) quinoline (77.8 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℃for 72 hours, cooled to room temperature and the solvent was distilled off under reduced pressure, separated by a 300-400 mesh silica gel column chromatography, petroleum ether: dichloromethane=10:1 elution, and vacuum drying to obtain the product with yield of 49% and enantiomer excess value of 97%. 1 H NMR (500 MHz, CDCl 3 )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, CDCl 3 )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, CDCl 3 )δ -15.48.
EXAMPLE 21 Synthesis of (R, E) - (2- (2- (but-2-en-2-yl) dibenzo [ b, d ] furan-1-yl) phenyl) diphenylphosphine
25 In a mL Schlenk tube, in a 25.0mL dry Schlenk tube with stirring bar, 2.0mL toluene was added (1, 5-Ring under ArOctadiene) Iridium (I) chloride dimer (3.4 mg,0.01 mmol,0.05 eq) and (R) PotentillaN-dimethyl- [ (S) -1,1 '-spiroindan-7, 7' -diyl]Phosphoramidite (7.3 mg,0.022 mmol,0.11 eq). The resulting mixed solution was stirred at room temperature for 1h. Then under argon (2- (dibenzo [ b, d)]Furan-1-yl) phenyl) diphenylphosphine (85.6 mg,0.2 mmol) and 2-butyne (54.0 mg,1.0 mmol), the resulting mixture was stirred at 70 ℃ for 72 hours, cooled to room temperature, the solvent was distilled off under reduced pressure, and separated by 300-400 mesh silica gel chromatography column, petroleum ether: dichloromethane=10:1 elution, and vacuum drying to obtain the product with yield of 84% and enantiomer excess value of 98%. 1 H NMR (500 MHz, CDCl 3 )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); 13 C NMR (126 MHz, CDCl 3 )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= 12.7 Hz), 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, CDCl 3 )δ -15.33.
EXAMPLE 22 Synthesis of (R, E) -1- (2- (but-2-en-2-yl) naphthalen-1-yl) -2- (diphenylphosphino) pyrrole
25 In a mL Schlenk tube, bis (1, 5-cyclooctadiene) -iridium triflate (3.4 mg,0.01 mmol,0.05 eq) and (R) are added to 2.0mL1, 4-dioxane under Ar in a 25.0mL dry Schlenk tube with stirring bar N-dimethyl- [ (S) -1,1 '-spiroindan-7, 7' -diyl]Phosphoramidite (7.3 mg,0.022 mmol,0.11 eq). The mixture to be formedThe combined solution was stirred at room temperature for 1h. 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℃for 72 hours, cooled to room temperature and the solvent was distilled off under reduced pressure, separated by a 300-400 mesh silica gel column chromatography, petroleum ether: dichloromethane=10:1 elution, and vacuum drying to obtain the product with yield of 69% and enantiomer excess value of 96%. 1 H NMR (500 MHz, CDCl 3 )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= 6.9 Hz, 3H); 13 C NMR (126 MHz, CDCl 3 )δ 141.6, 138.8 (d,J= 6.9 Hz), 137.8 (d,J= 6.4 Hz), 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, CDCl 3 )δ -33.62.
EXAMPLE 23 Synthesis of (R, E) - (2- (2- (but-2-en-2-yl) naphthalen-1-yl) phenyl) bis (4-fluorophenyl) phosphine
25 In a mL Schlenk tube, in a 25.0mL dry Schlenk tube with stirring bar, (1, 5-cyclooctadiene) iridium (I) chloride dimer (3.4 mg,0.01 mmol,0.05 eq) and (R) are added to 2.0mL toluene under ArN-dimethyl- [ (S) -1,1 '-spiroindan-7, 7' -diyl]Phosphoramidite (7.3 mg,0.022 mmol,0.11 eq). The resulting mixed solution was stirred at room temperature for 1h. 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 ℃ for 72 hours, cooled to room temperature and the solvent was distilled off under reduced pressure, separated by 300-400 mesh silica gel chromatography column, petroleum ether: dichloromethane=10:1 elution, and vacuum drying to obtain the product with yield of 52% and enantiomer excess value of 97%. 1 H NMR (500 MHz, CDCl 3 )δ 7.85 (d,J= 8.4 Hz, 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, CDCl 3 )δ 163.9 (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= 7.5 Hz), 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, CDCl 3 )δ -112.90 (d, J = 4.3 Hz, 1F), -113.78 (d, J = 5.2 Hz, 1F); 31 P NMR (202 MHz, CDCl 3 )δ -17.63.
EXAMPLE 24 Synthesis of (R, E) - (2- (2- (but-2-en-2-yl) naphthalen-1-yl) phenyl) bis (thiophen-2-yl) phosphine
25 In a mL Schlenk tube, in a 25.0mL dry Schlenk tube with stirring bar, (1, 5-cyclooctadiene) iridium (I) chloride dimer (3.4 mg,0.01 mmol,0.05 eq) and (R) are added to 2.0mL toluene under ArN-dimethyl- [ (S) -1,1 '-spiroindan-7, 7' -diyl]Phosphoramidite (7.3 mg,0.022 mmol,0.11 eq). The resulting mixed solution was stirred at room temperature for 1h. (2- (naphthalen-1-yl) phenyl) bis (thiophen-2-yl) phosphine (80.0 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℃for 72 hours, cooled to room temperature, the solvent was distilled off under reduced pressure, and separated by 300-400 mesh silica gel column chromatography, petroleum ether: dichloromethane=10:1 elution, and the product is obtained after vacuum drying, and the yield is 74% and an enantiomeric excess of 95%. 1 H NMR (500 MHz, CDCl 3 )δ 7.87 (d,J= 8.4 Hz, 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= 8.4 Hz, 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, CDCl 3 )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= 22.5 Hz), 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, CDCl 3 )δ -41.90.
EXAMPLE 25 Synthesis of (R, E) - (2- (2- (hexyl-3-en-3-yl) naphthalen-1-yl) phenyl) diphenylphosphine
25 In a mL Schlenk tube, in a 25.0mL dry Schlenk tube with stirring bar, (1, 5-cyclooctadiene) iridium (I) chloride dimer (3.4 mg,0.01 mmol,0.05 eq) and (R) are added to 2.0mL toluene under Ar N-dimethyl- [ (S) -1,1 '-spiroindan-7, 7' -diyl]Phosphoramidite (7.3 mg,0.022 mmol,0.11 eq). The resulting mixed solution was stirred at room temperature for 1h. (2- (naphthalen-1-yl) phenyl) diphenylphosphine (77.6 mg,0.2 mmol) and 3-hexyne (82.0 mg,1.0 mmol) were then added under argon, the resulting mixture was stirred at 70℃for 72 hours, cooled to room temperature and the solvent was distilled off under reduced pressure, separated by 300-400 mesh silica gel chromatography column, petroleum ether: dichloromethane=10:1 elution, and vacuum drying to obtain the product with 99% yield and 91% enantiomer excess. 1 H NMR (500 MHz, CDCl 3 )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, CDCl 3 )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= 12.1 Hz), 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= 10.4 Hz), 127.3, 126.9, 124.9 (d,J= 41.6 Hz), 24.2, 21.2, 14.2, 13.5; 31 P NMR (202 MHz, CDCl 3 )δ -15.48.
EXAMPLE 26 Synthesis of (R, E) - (2- (2- (oct-4-en-4-yl) naphthalen-1-yl) phenyl) diphenylphosphine
25 In a mL Schlenk tube, in a 25.0mL dry Schlenk tube with stirring bar, (1, 5-cyclooctadiene) iridium (I) chloride dimer (3.4 mg,0.01 mmol,0.05 eq) and (R) are added to 2.0mL toluene under ArN-dimethyl- [ (S) -1,1 '-spiroindan-7, 7' -diyl]Phosphoramidite (7.3 mg,0.022 mmol,0.11 eq). The resulting mixed solution was stirred at room temperature for 1h. (2- (naphthalen-1-yl) phenyl) diphenylphosphine (77.6 mg,0.2 mmol) and 4-octyne (110.2 mg,1.0 mmol) were then added under argon, the resulting mixture was stirred at 70 ℃ for 72 hours, cooled to room temperature, the solvent was distilled off under reduced pressure, and separated by 300-400 mesh silica gel chromatography column, petroleum ether: dichloromethane=10:1 elution, and vacuum drying to obtain the product with 53% yield and 85% enantiomer excess. 1 H NMR (500 MHz, CDCl 3 )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, CDCl 3 )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), 128.2, 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, CDCl 3 )δ -15.48.
EXAMPLE 27 Synthesis of (R, E) - (2- (2- (2, 9-dimethyldec-5-en-5-yl) naphthalen-1-yl) phenyl) diphenylphosphine
25 In a mL Schlenk tube, in a 25.0mL dry Schlenk tube with stirring bar, (1, 5-cyclooctadiene) iridium (I) chloride dimer (3.4 mg,0.01 mmol,0.05 eq) and (R) are added to 2.0mL toluene under ArN-dimethyl- [ (S) -1,1 '-spiroindan-7, 7' -diyl]Phosphoramidite (7.3 mg,0.022 mmol,0.11 eq). The resulting mixed solution was stirred at room temperature for 1h. (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 then added under argon, the resulting mixture was stirred at 70 ℃ for 72 hours, cooled to room temperature, the solvent was distilled off under reduced pressure, separated by 300-400 mesh silica gel chromatography column, petroleum ether: dichloromethane=10:1 elution, and vacuum drying to obtain the product with yield of 33% and enantiomer excess value of 93%. 1 H NMR (500 MHz, CDCl 3 )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, CDCl 3 )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, CDCl 3 )δ -15.45.
EXAMPLE 28 Synthesis of (R, E) -diphenyl (2- (2- (1-phenylpropyl-1-en-2-yl) naphthalen-1-yl) phenyl) phosphine
25 In a mL Schlenk tube, in a 25.0mL dry Schlenk tube with stirring bar, (1, 5-cyclooctadiene) iridium (I) chloride dimer (3.4 mg,0.01 mmol,0.05 eq) and (R) are added to 2.0mL toluene under Ar N-dimethyl- [ (S) -1,1 '-spiroindan-7, 7' -diyl]Phosphoramidite (7.3 mg,0.022 mmol,0.11 eq). The resulting mixed solution was stirred at room temperature for 1h. (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 then added under argon, the resulting mixture was stirred at 90 ℃ for 72 hours, cooled to room temperature and then distilled off under reduced pressure to remove the solvent, separated by 300-400 mesh silica gel chromatography column, petroleum ether: dichloromethane=10:1 elution, and vacuum drying to obtain the product with yield of 32% and enantiomer excess value of 89%. 1 H NMR (500 MHz, CDCl 3 )δ 7.89 (d,J= 8.6 Hz, 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, CDCl 3 )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= 13.2 Hz), 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, CDCl 3 )δ -15.29.
EXAMPLE 29 Synthesis of ethyl (R) -3- (1- (2- (diphenylphosphino) phenyl) naphthalen-2-yl) propionate
25 In a mL Schlenk tube, 1, 5-cyclooctadiene) iridium (I) chloride dimer (3.4 mg,0.01 mmol,0.05 eq) and (R) - (-) - (3, 5-dioxo-4-phosphorus-cycloheptyl [2,1-A,3,4-A ') were added to 2.0mL toluene under Ar in a 25.0mL dry Schlenk tube with stirring bar']Dinaphthyl) dimethylamine (8.0 mg,0.022 mmol,0.11 eq). The resulting mixed solution was stirred at room temperature for 1h. (2- (naphthalen-1-yl) phenyl) diphenylphosphine (77.6 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 ℃ for 48 hours, cooled to room temperature and the solvent was distilled off under reduced pressure, separated by 300-400 mesh silica gel chromatography column, petroleum ether: ethyl acetate=20:1, and the product is obtained after vacuum drying, the yield is 77%, and the enantiomer excess value is 91%. 1 H NMR (400 MHz, CDCl 3 )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, CDCl 3 )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, CDCl 3 )δ -15.39.
EXAMPLE 30 Synthesis of ethyl (R) -3- (1- (2- (diphenylphosphino) -5-methylphenyl) naphthalen-2-yl) propionate
25 In a mL Schlenk tube, 1, 5-cyclooctadiene) iridium (I) chloride dimer (3.4 mg,0.01 mmol,0.05 eq) and (R) - (-) - (3, 5-dioxo-4-phosphorus-cycloheptyl [2,1-A,3,4-A ') were added to 2.0mL toluene under Ar in a 25.0mL dry Schlenk tube with stirring bar']Dinaphthyl) dimethylamine (8.0 mg,0.022 mmol,0.11 eq). The resulting mixed solution was stirred at room temperature for 1h. (5-methyl-2- (naphthalen-1-yl) phenyl) diphenylphosphine (80.4 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 ℃ for 48 hours, cooled to room temperature and then the solvent was distilled off under reduced pressure, separated by 300-400 mesh silica gel chromatography column, petroleum ether: ethyl acetate=20:1, and the product is obtained after vacuum drying, the yield is 64%, and the enantiomer excess value is 90%. 1 H NMR (500 MHz, CDCl 3 )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, CDCl 3 )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= 2.3 Hz), 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 P NMR (202 MHz, CDCl 3 )δ -16.60.
EXAMPLE 31 Synthesis of ethyl (R) -3- (1- (2- (diphenylphosphino) -4-methylphenyl) naphthalen-2-yl) propionate
25 In a mL Schlenk tube, 2.0mL tetrahydrofuran was added under Ar in a 25.0mL dry Schlenk tube with stirring barTo (1, 5-cyclooctadiene) Iridium (I) chloride dimer (3.4 mg,0.01 mmol,0.05 eq) and (R) - (-) - (3, 5-dioxo-4-phosphorus-cycloheptyl [2,1-A,3,4-A ]' ]Dinaphthyl) dimethylamine (8.0 mg,0.022 mmol,0.11 eq). The resulting mixed solution was stirred at room temperature for 1h. (4-methyl-2- (naphthalen-1-yl) phenyl) diphenylphosphine (80.4 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 ℃ for 48 hours, cooled to room temperature and then distilled off under reduced pressure to remove the solvent, separated by 300-400 mesh silica gel chromatography column, petroleum ether: ethyl acetate=20:1, and the product is obtained after vacuum drying, the yield is 80%, and the enantiomer excess value is 99%. 1 H NMR (500 MHz, CDCl 3 )δ 7.70 (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, CDCl 3 )δ 173.0, 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 = 6.4 Hz), 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, CDCl 3 )δ -15.22.
EXAMPLE 32 Synthesis of ethyl (R) -3- (1- (2- (diphenylphosphino) phenyl) -4-methylnaphthalen-2-yl) propionate
25 In a mL Schlenk tube, in a 25.0mL dry Schlenk tube with stirring bar, (1, 5-cyclooctadiene) iridium (I) chloride dimer (3.4 mg,0.01 mmol,0.05 eq) and (R) - (-) - (3, 5-dioxo-4-phosphorus-cycloheptyl [2,1-A,3,4-A']dinaphthyl) dimethylamine (8.0 mg,0.022 mmol,0.11 eq). The resulting mixed solution was stirred at room temperature for 1h. (2- (4-methylnaphthalen-1-yl) phenyl) diphenylphosphine (80.4 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 ℃ for 48 hours, cooled to room temperature and then the solvent was distilled off under reduced pressure, separated by 300-400 mesh silica gel chromatography column, petroleum ether: ethyl acetate=20:1, and the product is obtained after vacuum drying, the yield is 66%, and the enantiomer excess value is 93%. 1 H NMR (400 MHz, CDCl 3 )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).; 13 C NMR (126 MHz, CDCl 3 ) 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= 7.2 Hz), 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 (162 MHz, CDCl 3 )δ -15.72.
EXAMPLE 33 Synthesis of ethyl (R) -3- (1- (2- (diphenylphosphino) -4, 5-dimethylphenyl) naphthalen-2-yl) propionate
25 In a mL Schlenk tube, 1, 5-cyclooctadiene) iridium (I) chloride dimer (3.4 mg,0.01 mmol,0.05 eq) and (R) - (-) - (3, 5-dioxo-4-phosphorus-cycloheptyl [2,1-A,3,4-A ') were added to 2.0mL toluene under Ar in a 25.0mL dry Schlenk tube with stirring bar']Dinaphthyl) dimethylamine (8.0 mg,0.022 mmol,0.11 eq). The resulting mixed solution was stirred at room temperature for 1h. Then (4, 5-dimethyl-2- (naphthalene-1-)) is added under argonPhenyl) diphenylphosphine (83.2 mg,0.2 mmol) and ethyl acrylate (100.0 mg,1.0 mmol), the resulting mixture was stirred at 150 ℃ for 48 hours, cooled to room temperature, the solvent was distilled off under reduced pressure, separated by 300-400 mesh silica gel column chromatography, petroleum ether: ethyl acetate=20:1, and the product is obtained after vacuum drying, the yield is 56%, and the enantiomer excess value is 88%. 1 H NMR (500 MHz, CDCl 3 )δ 7.80 (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, CDCl 3 ) 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= 6.4 Hz), 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, CDCl 3 )δ -16.52.
EXAMPLE 34 Synthesis of ethyl (R) -3- (1- (2- (diphenylphosphino) phenyl) -4-phenylnaphthalen-2-yl) propionate
25 In a mL Schlenk tube, 1, 5-cyclooctadiene) iridium (I) chloride dimer (3.4 mg,0.01 mmol,0.05 eq) and (R) - (-) - (3, 5-dioxo-4-phosphorus-cycloheptyl [2,1-A,3,4-A ') were added to 2.0mL toluene under Ar in a 25.0mL dry Schlenk tube with stirring bar' ]Dinaphthyl) dimethylamine (8.0 mg,0.022 mmol,0.11 eq). The resulting mixed solution was stirred at room temperature for 1h. Then diphenyl (2- (4-phenylnaphthalen-1-yl) phenyl) phosphine (92.8 mg,0.2 mmol) and ethyl acrylate (100.0 mg,1.0 mmol) were added under argon, the resulting mixture was stirred at 150℃for 48 hours, cooled to room temperature, the solvent was distilled off under reduced pressure, separated by a 300-400 mesh silica gel column,petroleum ether: ethyl acetate=20:1, and the product is obtained after vacuum drying, the yield is 55%, and the enantiomer excess value is 93%. 1 H NMR (500 MHz, CDCl 3 )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, CDCl 3 )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, CDCl 3 )δ -15.10.
EXAMPLE 35 Synthesis of ethyl (R) -3- (1- (2- (diphenylphosphino) -5-methoxyphenyl) naphthalen-2-yl) propionate
25 In a mL Schlenk tube, 1, 5-cyclooctadiene) iridium (I) chloride dimer (3.4 mg,0.01 mmol,0.05 eq) and (R) - (-) - (3, 5-dioxo-4-phosphorus-cycloheptyl [2,1-A,3,4-A ') were added to 2.0mL toluene under Ar in a 25.0mL dry Schlenk tube with stirring bar']Dinaphthyl) dimethylamine (8.0 mg,0.022 mmol,0.11 eq). The resulting mixed solution was stirred at room temperature for 1h. (4-methoxy-2- (naphthalen-1-yl) phenyl) diphenylphosphine (83.6 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 ℃ for 48 hours, cooled to room temperature and then distilled off under reduced pressure to remove the solvent, separated by 300-400 mesh silica gel chromatography column, petroleum ether: ethyl acetate=20:1, and the product is obtained after vacuum drying, the yield is 68%, and the enantiomer excess value is 82%. 1 H NMR (500 MHz, CDCl 3 )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, CDCl 3 ) 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= 6.9 Hz), 114.2, 60.2, 55.2, 35.1, 28.7, 14.1; 31 P NMR (202 MHz, CDCl 3 )δ -17.63.
EXAMPLE 36 Synthesis of ethyl (R) -3- (1- (2- (diphenylphosphino) phenyl) -4-methoxynaphthalen-2-yl) propionate
25 In a mL Schlenk tube, 1, 5-cyclooctadiene) iridium (I) chloride dimer (3.4 mg,0.01 mmol,0.05 eq) and (R) - (-) - (3, 5-dioxo-4-phosphorus-cycloheptyl [2,1-A,3,4-A ') were added to 2.0mL toluene under Ar in a 25.0mL dry Schlenk tube with stirring bar']Dinaphthyl) dimethylamine (8.0 mg,0.022 mmol,0.11 eq). The resulting mixed solution was stirred at room temperature for 1h. (2- (4-methoxynaphthalen-1-yl) phenyl) diphenylphosphine (83.6 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 ℃ for 48 hours, cooled to room temperature and then the solvent was distilled off under reduced pressure, separated by 300-400 mesh silica gel chromatography column, petroleum ether: ethyl acetate=20:1, and the product is obtained after vacuum drying, the yield is 21%, and the enantiomer excess value is 90%. 1 H NMR (500 MHz, CDCl 3 )δ8.19 (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, CDCl 3 )δ173.0, 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, CDCl 3 )δ -15.48.
EXAMPLE 37 Synthesis of Ethyl (R) -3- (1- (6- (diphenylphosphino) benzo [ d ] [1,3] dioxo-5-yl) naphthalen-2-yl) propionate
25 In a mL Schlenk tube, 1, 5-cyclooctadiene) iridium (I) chloride dimer (3.4 mg,0.01 mmol,0.05 eq) and (R) - (-) - (3, 5-dioxo-4-phosphorus-cycloheptyl [2,1-A,3,4-A ') were added to 2.0mL toluene under Ar in a 25.0mL dry Schlenk tube with stirring bar' ]Dinaphthyl) dimethylamine (8.0 mg,0.022 mmol,0.11 eq). The resulting mixed solution was stirred at room temperature for 1h. (6- (naphthalen-1-yl) benzo [ d ] is then added under argon][1,3]Dihydroxy-5-yl) diphenylphosphine (86.2 mg,0.2 mmol) and ethyl acrylate (100.0 mg,1.0 mmol), the resulting mixture was stirred at 150℃for 48 hours, cooled to room temperature, the solvent was distilled off under reduced pressure, and separated by a 300-400 mesh silica gel column, petroleum ether: ethyl acetate=20:1, and the product is obtained after vacuum drying, the yield is 56%, and the enantiomer excess value is 88%. 1 H NMR (500 MHz, CDCl 3 )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, CDCl 3 )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= 6.4 Hz), 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= 2.9 Hz), 14.3; 31 P NMR (202 MHz, CDCl 3 )δ -15.49.
EXAMPLE 38 Synthesis of ethyl (R) -3- (1- (2- (diphenylphosphino) -4-fluorophenyl) naphthalen-2-yl) propionate
25 In a mL Schlenk tube, iridium (I) chloride dimer (3.4 mg,0.01 mmol,0.05 eq) and (R) - (-) - (3, 5-dioxo-4-phosphorus-cycloheptyl [2,1-A,3,4-A ') were added to 2.0mL o-xylene under Ar in a 25.0mL dry Schlenk tube with stirring bar']Dinaphthyl) dimethylamine (8.0 mg,0.022 mmol,0.11 eq). The resulting mixed solution was stirred at room temperature for 1h. (5-fluoro-2- (naphthalen-1-yl) phenyl) diphenylphosphine (81.2 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 ℃ for 48 hours, cooled to room temperature and then the solvent was distilled off under reduced pressure, separated by 300-400 mesh silica gel chromatography column, petroleum ether: ethyl acetate=20:1, and the product is obtained after vacuum drying, the yield is 77%, and the enantiomer excess value is 92%. 1 H NMR (500 MHz, CDCl 3 )δ7.81 (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, CDCl 3 ) δ172.9, 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 (202 MHz, CDCl 3 )δ -14.68.
EXAMPLE 39 Synthesis of ethyl (R) -3- (1- (2- (diphenylphosphino) -4, 5-difluorophenyl) naphthalen-2-yl) propionate
25 In a mL Schlenk tube, 1, 5-cyclooctadiene) iridium (I) chloride dimer (3.4 mg,0.01 mmol,0.05 eq) and (R) - (-) - (3, 5-dioxo-4-phosphorus-cycloheptyl [2,1-A,3,4-A ') were added to 2.0mL toluene under Ar in a 25.0mL dry Schlenk tube with stirring bar']Dinaphthyl) dimethylamine (8.0 mg,0.022 mmol,0.11 eq). The resulting mixed solution was stirred at room temperature for 1h. (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 then added under argon, the resulting mixture was stirred at 150 ℃ for 48 hours, cooled to room temperature, the solvent was distilled off under reduced pressure, and separated by 300-400 mesh silica gel chromatography column, petroleum ether: ethyl acetate=20:1, and the product is obtained after vacuum drying, the yield is 23%, and the enantiomer excess value is 93%. 1 H NMR (500 MHz, CDCl 3 )δ7.83 (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, CDCl 3 )δ 172.7, 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= 4.3 Hz), 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, CDCl 3 )δ -16.02.
EXAMPLE 40 Synthesis of ethyl (R) -3- (1- (5-chloro-2- (diphenylphosphino) phenyl) naphthalen-2-yl) propionate
25 In a mL Schlenk tube, 1, 5-cyclooctadiene) iridium (I) chloride dimer (3.4 mg,0.01 mmol,0.05 eq) and (R) - (-) - (3, 5-dioxo-4-phosphorus-cycloheptyl [2,1-A,3,4-A ') were added to 2.0mL toluene under Ar in a 25.0mL dry Schlenk tube with stirring bar' ]Dinaphthyl) dimethylamine (8.0 mg,0.022 mmol,0.11 eq). The resulting mixed solution was stirred at room temperature for 1h. (4-chloro-2- (naphthalen-1-yl) phenyl) diphenylphosphine (84.4 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 ℃ for 48 hours, cooled to room temperature and then the solvent was distilled off under reduced pressure, separated by 300-400 mesh silica gel chromatography column, petroleum ether: ethyl acetate=20:1, and the product is obtained after vacuum drying, the yield is 51%, and the enantiomer excess value is 90%. 1 H NMR (500 MHz, CDCl 3 )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, CDCl 3 ) 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= 1.8 Hz), 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, CDCl 3 )δ -16.63.
EXAMPLE 41 Synthesis of ethyl (R) -3- (4-chloro-1- (2- (diphenylphosphino) phenyl) naphthalen-2-yl) propionate
25 In a mL Schlenk tube, 1, 5-cyclooctadiene) iridium (I) chloride dimer (3.4 mg,0.01 mmol,0.05 eq) and (R) - (-) - (3, 5-dioxo-4-phosphorus-cycloheptyl [2,1-A,3,4-A ') were added to 2.0mL toluene under Ar in a 25.0mL dry Schlenk tube with stirring bar']Dinaphthyl) dimethylamine (8.0 mg,0.022 mmol,0.11 eq). The resulting mixed solution was stirred at room temperature for 1h. (2- (4-chloronaphthalen-1-yl) phenyl) diphenylphosphine (84.4 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 ℃ for 48 hours, cooled to room temperature and then the solvent was distilled off under reduced pressure, separated by 300-400 mesh silica gel chromatography column, petroleum ether: ethyl acetate=20:1, and the product is obtained after vacuum drying, the yield is 75%, and the enantiomer excess value is 93%. 1 H NMR (500 MHz, CDCl 3 )δ8.22 (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, CDCl 3 ) δ172.6, 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= 9.2 Hz), 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; 31 P NMR (202 MHz, CDCl 3 )δ -15.50.
EXAMPLE 42 Synthesis of ethyl (R) -3- (1- (2- (diphenylphosphino) -5- (trifluoromethyl) phenyl) naphthalen-2-yl) propionate
25 In a mL Schlenk tube, 1, 5-cyclooctadiene) iridium (I) chloride dimer (3.4 mg,0.01 mmol,0.05 eq) and (R) - (-) - (3, 5-dioxo-4-phosphorus-cycloheptyl [2,1-A,3,4-A ') were added to 2.0mL toluene under Ar in a 25.0mL dry Schlenk tube with stirring bar']Dinaphthyl) dimethylamine (8.0 mg,0.022 mmol,0.11 eq). The resulting mixed solution was stirred at room temperature for 1h. (2- (naphthalen-1-yl) -4- (trifluoromethyl) phenyl) diphenylphosphine (91.2 mg,0.2 mmol) and ethyl acrylate (100.0 mg,1.0 mmol) were then added under argon and the resulting mixture stirred at 150 ℃ for 48 hours, cooled to room temperature and then distilled off under reduced pressure to remove the solvent, separated by a 300-400 mesh silica gel column chromatography, petroleum ether: ethyl acetate=20:1, and the product is obtained after vacuum drying, the yield is 43%, and the enantiomer excess value is 90%. 1 H NMR (500 MHz, CDCl 3 )δ7.84 (d,J= 8.5 Hz, 1H), 7.78 (dd,J= 8.2, 1.5 Hz, 1H), 7.64 (dd,J= 8.2, 2.2 Hz, 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, CDCl 3 )δ 172.7, 145.6 (d,J= 32.9 Hz), 144.1 (d,J= 16.8 Hz), 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= 32.4 Hz), 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, CDCl 3 )δ -15.19; 19 F NMR (471 MHz, CDCl 3 )δ -62.59.
EXAMPLE 43 Synthesis of ethyl (R) -3- (1- (2- (diphenylphosphino) -4- (trifluoromethyl) phenyl) naphthalen-2-yl) propionate
25 In a mL Schlenk tube, 1, 5-cyclooctadiene) iridium (I) chloride dimer (3.4 mg,0.01 mmol,0.05 eq) and (R) - (-) - (3, 5-dioxo-4-phosphorus-cycloheptyl [2,1-A,3,4-A ') were added to 2.0mL toluene under Ar in a 25.0mL dry Schlenk tube with stirring bar' ]Dinaphthyl) dimethylamine (8.0 mg,0.022 mmol,0.11 eq). The resulting mixed solution was stirred at room temperature for 1h. (2- (naphthalen-1-yl) -5- (trifluoromethyl) phenyl) diphenylphosphine (91.2 mg,0.2 mmol) and ethyl acrylate (100.0 mg,1.0 mmol) were then added under argon and the resulting mixture stirred at 150 ℃ for 48 hours, cooled to room temperature and then the solvent was distilled off under reduced pressure and separated by a 300-400 mesh silica gel column, petroleum ether: ethyl acetate=20:1, and the product is obtained after vacuum drying, the yield is 48%, and the enantiomer excess value is 99%. 1 H NMR (500 MHz, CDCl 3 )δ 7.84 (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, CDCl 3 ) δ172.7, 148.8 (d,J= 32.4 Hz), 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= 2.3 Hz), 132.5 (d,J= 2.3 Hz), 131.9, 131.4 (d,J= 5.2 Hz), 130.4 (q,J= 4.7, 4.2 Hz), 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= 3.5 Hz), 125.2, 60.4, 35.0, 28.8 (d,J= 2.9 Hz), 14.2; 31 P NMR (202 MHz, CDCl 3 )δ -14.84; 19 F NMR (471 MHz, CDCl 3 )δ -108.22.
EXAMPLE 44 Synthesis of ethyl (R) -3- (5- (2- (diphenylphosphino) phenyl) -1, 2-dihydroacenaphthylen-4-yl) propionate
25 In a mL Schlenk tube, iridium (I) chloride dimer (3.4 mg,0.01 mmol,0.05 eq) and (R) - (-) - (3, 5-dioxo-4-phosphorus-cycloheptyl [2,1-A,3,4-A ') were added to 2.0mL metaxylene under Ar in a 25.0mL dry Schlenk tube with stirring bar']Dinaphthyl) dimethylamine (8.0 mg,0.022 mmol,0.11 eq). The resulting mixed solution was stirred at room temperature for 1h. (2- (1, 2-Acenaphthylen-5-yl) phenyl) diphenylphosphine (82.8 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℃for 48 hours, cooled to room temperature, the solvent was distilled off under reduced pressure, and separated by 300-400 mesh silica gel column chromatography, petroleum ether: ethyl acetate=20:1, and the product is obtained after vacuum drying, the yield is 61%, and the enantiomer excess value is 93%. 1 H NMR (500 MHz, CDCl 3 )δ7.44 (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, CDCl 3 ) δ 173.0, 145.7 (d,J= 66.5 Hz), 145.1 (d,J= 33.5 Hz), 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, CDCl 3 )δ -15.59.
EXAMPLE 45 Synthesis of ethyl (R) -3- (10- (2- (diphenylphosphino) phenyl) phenanthren-9-yl) propionate
25 In a mL Schlenk tube, 1, 5-cyclooctadiene) iridium (I) chloride dimer (3.4 mg,0.01 mmol,0.05 eq) and (R) - (-) - (3, 5-dioxo-4-phosphorus-cycloheptyl [2,1-A,3,4-A ') were added to 2.0mL toluene under Ar in a 25.0mL dry Schlenk tube with stirring bar']Dinaphthyl) dimethylamine (8.0 mg,0.022 mmol,0.11 eq). The resulting mixed solution was stirred at room temperature for 1h. (2- (phenanthren-9-yl) phenyl) diphenylphosphine (87.6 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 ℃ for 48 hours, cooled to room temperature, the solvent was distilled off under reduced pressure, and separated by a 300-400 mesh silica gel column chromatography, petroleum ether: ethyl acetate=20:1, and the product is obtained after vacuum drying, the yield is 51%, and the enantiomer excess value is 90%. 1 H NMR (500 MHz, CDCl 3 )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, CDCl 3 )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= .2 Hz), 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, CDCl 3 )δ -15.33.
EXAMPLE 46 Synthesis of Ethyl (R) -3- (1- (2- (diphenylphosphino) phenyl) pyren-2-yl) propionate
25 In a mL Schlenk tube, 1, 5-cyclooctadiene) iridium (I) chloride dimer (3.4 mg,0.01 mmol,0.05 eq) and (R) - (-) - (3, 5-dioxo-4-phosphorus-cycloheptyl [2,1-A,3,4-A ') were added to 2.0mL toluene under Ar in a 25.0mL dry Schlenk tube with stirring bar' ]Dinaphthyl) dimethylamine (8.0 mg,0.022 mmol,0.11 eq). The resulting mixed solution was stirred at room temperature for 1h. Diphenyl (2- (pyren-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 ℃ for 48 hours, cooled to room temperature and the solvent was distilled off under reduced pressure, separated by 300-400 mesh silica gel chromatography column, petroleum ether: ethyl acetate=20:1, and the product is obtained after vacuum drying, the yield is 58%, and the enantiomer excess value is 86%. 1 H NMR (500 MHz, CDCl 3 )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, CDCl 3 )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, CDCl 3 )δ -15.27.
EXAMPLE 47 Synthesis of ethyl (R) -3- (3 '- (diphenylphosphino) - [1,2' -binaphthyl ] -2-yl) propionate
25 In a mL Schlenk tube, 1, 5-cyclooctadiene) iridium (I) chloride dimer (3.4 mg,0.01 mmol,0.05 eq) and (R) - (-) - (3, 5-dioxo-4-phosphorus-cycloheptyl [2,1-A,3,4-A ') were added to 2.0mL toluene under Ar in a 25.0mL dry Schlenk tube with stirring bar']Dinaphthyl) dimethylamine (8.0 mg,0.022 mmol,0.11 eq). The resulting mixed solution was stirred at room temperature for 1h. Then adding [1,2' -binaphthyl ] under argon]-3' -diphenylphosphine (87.6 mg,0.2 mmol) and ethyl acrylate (100.0 mg,1.0 mmol), the resulting mixture was stirred at 150 ℃ for 48 hours, cooled to room temperature, the solvent was distilled off under reduced pressure, separated by 300-400 mesh silica gel column chromatography, petroleum ether: ethyl acetate=20:1, and the product is obtained after vacuum drying, the yield is 78%, and the enantiomer excess value is 91%. 1 H NMR (500 MHz, CDCl 3 )δ 7.82 (t,J= 9.2 Hz, 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, CDCl 3 ) 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= 1.8 Hz), 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, CDCl 3 )δ -14.28.
EXAMPLE 48 Synthesis of ethyl (S) -3- (4- (2- (diphenylphosphino) phenyl) quinolin-3-yl) propionate
25 In a mL Schlenk tube, 1, 5-cyclooctadiene) iridium (I) chloride dimer (3.4 mg,0.01 mmol,0.05 eq) and (R) - (-) - (3, 5-dioxo-4-phosphorus-cycloheptyl [2,1-A,3,4-A ') were added to 2.0mL toluene under Ar in a 25.0mL dry Schlenk tube with stirring bar']Dinaphthyl) dimethylamine (8.0 mg,0.022 mmol,0.11 eq). The resulting mixed solution was stirred at room temperature for 1h. 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 ℃ for 48 hours, cooled to room temperature and the solvent was distilled off under reduced pressure, separated by a 300-400 mesh silica gel column chromatography, petroleum ether: ethyl acetate=20:1, and the product is obtained after vacuum drying, the yield is 48%, and the enantiomer excess value is 91%. 1 H NMR (500 MHz, CDCl 3 ) 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, 1.5 Hz, 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, CDCl 3 ) δ172.4, 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= 2.9 Hz), 126.2 (d,J= 11.6 Hz), 60.5, 34.7, 26.4 (d,J= 2.9 Hz), 14.2; 31 P NMR (202 MHz, CDCl 3 )δ -15.15.
EXAMPLE 49 Synthesis of ethyl (R) -3- (1- (2- (diphenylphosphino) phenyl) dibenzo [ b, d ] furan-2-yl) propionate
25 In a mL Schlenk tube, in a 25.0mL dry Schlenk tube with stirring bar, inTo 2.0ml of toluene under Ar are added (1, 5-cyclooctadiene) iridium (I) chloride dimer (3.4 mg,0.01 mmol,0.05 eq) and (R) - (-) - (3, 5-dioxo-4-phosphorus-cycloheptyl [2,1-A,3,4-A ]' ]Dinaphthyl) dimethylamine (8.0 mg,0.022 mmol,0.11 eq). The resulting mixed solution was stirred at room temperature for 1h. Then under argon (2- (dibenzo [ b, d)]Furan-1-yl) phenyl) diphenylphosphine (85.6 mg,0.2 mmol) and ethyl acrylate (100.0 mg,1.0 mmol), the resulting mixture was stirred at 150 ℃ for 48 hours, cooled to room temperature, the solvent was distilled off under reduced pressure, separated by 300-400 mesh silica gel chromatography column, petroleum ether: ethyl acetate=20:1, and the product is obtained after vacuum drying, the yield is 57%, and the enantiomer excess value is 90%. 1 H NMR (500 MHz, CDCl 3 ) δ 7.53 – 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, CDCl 3 )δ 172.9, 156.3, 154.3, 144.0 (d,J= 32.4 Hz), 138.1(d,J= 13.3 Hz), 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= 3.5 Hz), 14.2; 31 P NMR (202 MHz, CDCl 3 )δ -14.16.
EXAMPLE 50 Synthesis of ethyl (R) -3- (1- (2- (bis (4-fluorophenyl) phosphino) phenyl) naphthalen-2-yl) propionate
25 In a mL Schlenk tube, bis (ethylene) iridium chloride dimer (3.4 mg,0.01 mmol,0.05 eq) and (R) - (-) - (3, 5-dioxo-4-phosphorus-cycloheptyl [2,1-A,3,4-A ') were added to 2.0mL paraxylene under Ar in a 25.0mL dry Schlenk tube with stirring bar']Dinaphthyl) dimethylamine (8.0 mg,0.022 mmol,0.11 eq). Dissolving the mixtureThe solution was stirred at room temperature for 1h. 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 then added under argon, the resulting mixture was stirred at 150 ℃ for 48 hours, cooled to room temperature and then the solvent was distilled off under reduced pressure, separated by 300-400 mesh silica gel chromatography column, petroleum ether: ethyl acetate=20:1, and the product is obtained after vacuum drying, the yield is 40%, and the enantiomer excess value is 95%. 1 H NMR (500 MHz, CDCl 3 ) 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, CDCl 3 )δ 172.8, 163.1 (d,J= 248.5 Hz), 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 = 7.9 Hz), 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, 7.5 Hz), 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, CDCl 3 )δ -17.50; 19 F NMR (471 MHz, CDCl 3 )δ -112.66 (d,J= 4.3 Hz), -112.79 (d,J= 4.3 Hz).
EXAMPLE 51 Synthesis of ethyl (R) -3- (1- (2- (di (thiophen-2-yl) phosphino) phenyl) naphthalen-2-yl) propionate
25 In a mL Schlenk tube, in a 25.0mL dry Schlenk tube with stirring bar, (1, 5-cyclooctadiene) iridium (I) chloride dimer (3.4 mg,0.01 mmol,0) was added to 2.0mL toluene under Ar.05 eq) and (R) - (-) - (3, 5-dioxo-4-phosphorus-cycloheptyl [2,1-A,3,4-A ]']Dinaphthyl) dimethylamine (8.0 mg,0.022 mmol,0.11 eq). The resulting mixed solution was stirred at room temperature for 1h. (2- (naphthalen-1-yl) phenyl) bis (thiophen-2-yl) phosphine (80.0 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 ℃ for 48 hours, cooled to room temperature and the solvent was distilled off under reduced pressure, separated by 300-400 mesh silica gel chromatography column, petroleum ether: ethyl acetate=20:1, and the product is obtained after vacuum drying, the yield is 37%, and the enantiomer excess value is 87%. 1 H NMR (500 MHz, CDCl 3 ) 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= 8.5 Hz, 1H), 6.83 – 6.79 (m, 1H), 6.76 (dd,J= 6.5, 3.1 Hz, 1H), 4.06 (q,J= 7.1 Hz, 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, CDCl 3 )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, CDCl 3 )δ -43.41; 19 F NMR (471 MHz, CDCl 3 )δ -112.66 (d,J= 4.3 Hz), -112.79 (d,J= 4.3 Hz).
EXAMPLE 52 Synthesis of methyl (R) -3- (1- (2- (diphenylphosphino) phenyl) naphthalen-2-yl) propionate
25 In a mL Schlenk tube, iridium (I) (3.4 mg,0.01 mmol,0.05 eq) and (R) bis (1, 5-cyclooctadiene) tetrafluoroborate were added to 2.0mL toluene under Ar in a 25.0mL dry Schlenk tube with stirring bar ) - (-) - (3, 5-dioxo-4-phospho-cycloheptyl [2,1-A,3,4-A ]']Dinaphthyl) dimethylamine (8.0 mg,0.022 mmol,0.11 eq). The resulting mixed solution was stirred at room temperature for 1h. (2- (naphthalen-1-yl) phenyl) diphenylphosphine (77.6 mg,0.2 mmol) and methyl acrylate (86.0 mg,1.0 mmol) were then added under argon, the resulting mixture was stirred at 150 ℃ for 48 hours, cooled to room temperature and the solvent was distilled off under reduced pressure, separated by 300-400 mesh silica gel chromatography column, petroleum ether: ethyl acetate=20:1, and the product is obtained after vacuum drying, the yield is 77%, and the enantiomer excess value is 82%. 1 H NMR (400 MHz, CDCl 3 ) 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); 13 C NMR (101 MHz, CDCl 3 ) 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= 2.3 Hz), 128.1 (d, J = 6.8 Hz), 128.0, 127.7 (d,J= 28.6 Hz), 126.4 (d,J= 10.0 Hz), 125.2 (d,J= 64.9 Hz), 51.4, 34.8, 28.8; 31 P NMR (162 MHz, CDCl 3 )δ -15.45.
EXAMPLE 53 Synthesis of tert-butyl (R) -3- (1- (2- (diphenylphosphino) phenyl) naphthalen-2-yl) propionate
25 In a mL Schlenk tube, 1, 5-cyclooctadiene) iridium (I) chloride dimer (3.4 mg,0.01 mmol,0.05 eq) and (R) - (-) - (3, 5-dioxo-4-phosphorus-cycloheptyl [2,1-A,3,4-A ') were added to 2.0mL toluene under Ar in a 25.0mL dry Schlenk tube with stirring bar']Dinaphthyl) dimethylamine (8.0 mg,0.022 mmol,0.11 eq). The resulting mixed solution was stirred at room temperature for 1h. (2- (naphthalen-1-yl) phenyl) diphenyl is then added under argonPhosphine (77.6 mg,0.2 mmol) and t-butyl acrylate (128.2 mg,1.0 mmol), the resulting mixture was stirred at 150 ℃ for 48 hours, cooled to room temperature and the solvent was distilled off under reduced pressure, separated by 300-400 mesh silica gel column chromatography, petroleum ether: ethyl acetate=20:1, and the product is obtained after vacuum drying, the yield is 59%, and the enantiomer excess value is 92%. 1 H NMR (500 MHz, CDCl 3 ) 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, CDCl 3 ) 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 P NMR (202 MHz, CDCl 3 )δ -15.40.
Example 542,2,2 Synthesis of trifluoroethyl (R) -3- (1- (2- (diphenylphosphino) phenyl) naphthalen-2-yl) propionate
25 In a mL Schlenk tube, 1, 5-cyclooctadiene) iridium (I) chloride dimer (3.4 mg,0.01 mmol,0.05 eq) and (R) - (-) - (3, 5-dioxo-4-phosphorus-cycloheptyl [2,1-A,3,4-A ') were added to 2.0mL toluene under Ar in a 25.0mL dry Schlenk tube with stirring bar']Dinaphthyl) dimethylamine (8.0 mg,0.022 mmol,0.11 eq). The resulting mixed solution was stirred at room temperature for 1h. (2- (naphthalen-1-yl) phenyl) diphenylphosphine (77.6 mg,0.2 mmol) and trifluoroethyl acrylate (154.1 mg,1.0 m) were then added under argonmol), stirring the obtained mixture at 150 ℃ for 48 hours, cooling to room temperature, removing the solvent by decompression and steaming, separating by a 300-400 mesh silica gel chromatographic column, and petroleum ether: ethyl acetate=20:1, and the product is obtained after vacuum drying, the yield is 51%, and the enantiomer excess value is 93%. 1 H NMR (500 MHz, CDCl 3 )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, CDCl 3 ) δ 171.2, 144.8 (d,J= 32.9 Hz), 138.4 (d,J= 12.1 Hz), 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= 16.8 Hz), 133.0 (d,J= 2.3 Hz), 131.9, 130.7 (d,J= 5.8 Hz), 129.1, 128.4 (d,J= 6.9 Hz), 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, CDCl 3 )δ -15.45; 19 F NMR (471 MHz, CDCl 3 )δ -73.66.
EXAMPLE 55 Synthesis of ethyl (R) -3- (2 '- (diphenylphosphino) - [1,1' -binaphthyl ] -2-yl) propionate
25 In a mL Schlenk tube, iridium (I) chloride dimer (3.4 mg,0.01 mmol,0.05 eq) and (R) - (-) - (3, 5-dioxo-4-phosphorus-cycloheptyl [2,1-A,3,4-A ') were added to 2.0mL benzotrifluoride under Ar in a 25.0mL dry Schlenk tube with stirring bar' ]Dinaphthyl) dimethylamine (8.0 mg,0.022 mmol,0.11 eq). The resulting mixed solution was stirred at room temperature for 1h. Then adding [1,1' -binaphthyl ] under argon]-2-diphenylphosphine (87.6 mg,0.2 mmol) and ethyl acrylate (100.0 mg,1.0 mmol), the resulting mixture was stirred at 150℃for 72 hours, cooled to room temperature, the solvent was distilled off under reduced pressure, and the solvent was removed by distillation under the reduced pressure, 30% was obtainedSeparating with 0-400 mesh silica gel chromatographic column, petroleum ether: ethyl acetate=20:1, and the product is obtained after vacuum drying, the yield is 43%, and the enantiomer excess value is 93%. 1 H NMR (400 MHz, CDCl 3 )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); 13 C NMR (101 MHz, CDCl 3 )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= 5.5 Hz), 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, CDCl 3 )δ -15.02.。
Claims (10)
1. A method for preparing a biphenyl or phenyl pyrrole chiral monophosphine ligand with a lipid chain substitution, which is characterized by comprising the following steps:
taking biphenyl type or phenyl pyrrole type monophosphine ligand as a raw material, controlling the reaction temperature to be 70-150 ℃ in an organic solution under the protection of inert gas, and carrying out asymmetric hydrocarbon activation reaction on the raw material and a lipid chain compound under the participation of chiral ligand by catalyst to obtain the lipid chain substituted biphenyl type or phenyl pyrrole type chiral monophosphine ligand;
the catalyst is monovalent iridium;
the aliphatic chain compound is aliphatic alkene, aliphatic alkyne or derivatives thereof;
structural formula of fatty olefin or derivative thereof Is that；
The structural formula of the aliphatic alkyne or the derivative thereof is；
R 4 Independently selected from ester groups, alkyl groups or aryl groups.
2. The process of claim 1, wherein R is 4 Selected from ester groups, C1-C5 alkyl groups or unsubstituted aryl groups.
3. The preparation method according to claim 1, wherein the monovalent iridium is one or more selected from (1, 5-cyclooctadiene) iridium (I) chloride dimer, bicyclooctenyl iridium (I) chloride dimer, bis (1, 5-cyclooctadiene) -iridium triflate, bis (1, 5-cyclooctadiene) iridium tetrafluoroborate (I) and bis (ethylene) iridium chloride dimer; preferably, the monovalent iridium is derived from (1, 5-cyclooctadiene) chloroiridium (I) dimer.
4. The preparation method of claim 1, wherein the molar ratio of the catalyst, chiral ligand, raw material and aliphatic chain compound is 5%:11%: 1:5-10.
5. The method according to claim 1, wherein the organic solvent is toluene, benzotrifluoride, paraxylene, metaxylene, orthoxylene, tetrahydrofuran, or a mixture of one or more of 1, 4-dioxane; the preferred organic solvent is toluene.
6. The preparation method according to claim 1, wherein the chiral ligand is selected from one of (R) - (-) - (3, 5-dioxo-4-phospho-cyclohepta [2,1-a,3,4-a '] dinaphthyl) dimethylamine, N-dimethyl- [ (R) -1,1' -spiroindan-7, 7 '-diyl ] phosphoramidite, (3 ar,8 ar) - (2, 2-dimethyl-4,4,8,8-tetraphenyl-tetrahydro- [1,3] dioxa [4,5-e ] [1,3,2] dioxaphosphepin-6-yl) dimethylamine or (R) - (+) - (3, 5-dioxa-4-phospho-cyclohepta [2,1-a;3,4-a' ] dinaphthyl-4-yl) -5 hydrogen-dibenzo [ b, f ] azepin; a preferred chiral ligand is (R) - (-) - (3, 5-dioxo-4-phospho-cycloheptyl [2,1-A,3,4-A' ] dinaphthyl) dimethylamine.
7. The method according to claim 1, wherein the inert gas is argon or nitrogen.
8. The method according to claim 1, wherein the reaction time is 48 to 72 hours.
9. The process of claim 1, wherein the starting material is selected from the group consisting of compounds of formula 1 and 11:
，/>，
wherein R is 1 Independently selected from substituted or unsubstituted aryl; r is R 2 、R 3 Independently selected from a hydrogen atom, 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.
10. The process of claim 9, wherein R 1 Selected from halogen substituted aryl or unsubstituted aryl; more preferably, R 1 Selected from halophenyl, phenyl, or thienyl.
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