CN114560893B - 平面手性茂金属化合物、其合成方法及应用 - Google Patents
平面手性茂金属化合物、其合成方法及应用 Download PDFInfo
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- CN114560893B CN114560893B CN202210262104.4A CN202210262104A CN114560893B CN 114560893 B CN114560893 B CN 114560893B CN 202210262104 A CN202210262104 A CN 202210262104A CN 114560893 B CN114560893 B CN 114560893B
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 110
- 238000010189 synthetic method Methods 0.000 title description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims abstract description 61
- 239000003446 ligand Substances 0.000 claims abstract description 49
- 239000010948 rhodium Substances 0.000 claims abstract description 39
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims abstract description 30
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- 239000003960 organic solvent Substances 0.000 claims abstract description 20
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 20
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000002360 preparation method Methods 0.000 claims abstract description 15
- 239000003513 alkali Substances 0.000 claims abstract description 12
- 238000006254 arylation reaction Methods 0.000 claims abstract description 11
- 230000001681 protective effect Effects 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 84
- -1 aliphatic radical Chemical class 0.000 claims description 83
- 125000000217 alkyl group Chemical group 0.000 claims description 61
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 39
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 39
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 32
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 31
- 229910052799 carbon Inorganic materials 0.000 claims description 30
- 125000005842 heteroatom Chemical group 0.000 claims description 30
- 125000001424 substituent group Chemical group 0.000 claims description 30
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 28
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 28
- 125000003118 aryl group Chemical group 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 25
- 239000002904 solvent Substances 0.000 claims description 22
- 125000001072 heteroaryl group Chemical group 0.000 claims description 21
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 18
- 229910052731 fluorine Inorganic materials 0.000 claims description 18
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 18
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 18
- 229910052740 iodine Inorganic materials 0.000 claims description 17
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 16
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 16
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 16
- 229910052717 sulfur Inorganic materials 0.000 claims description 16
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 16
- 229910052760 oxygen Inorganic materials 0.000 claims description 15
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 14
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 14
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 125000003342 alkenyl group Chemical group 0.000 claims description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 12
- 125000004429 atom Chemical group 0.000 claims description 11
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 11
- 125000000623 heterocyclic group Chemical group 0.000 claims description 11
- 150000003254 radicals Chemical class 0.000 claims description 11
- 125000002723 alicyclic group Chemical group 0.000 claims description 10
- 150000005840 aryl radicals Chemical class 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 10
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 9
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 9
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 8
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 8
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 8
- 125000006374 C2-C10 alkenyl group Chemical group 0.000 claims description 7
- 125000005865 C2-C10alkynyl group Chemical group 0.000 claims description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical class [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 7
- 125000000304 alkynyl group Chemical group 0.000 claims description 7
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 7
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 7
- 125000004972 1-butynyl group Chemical group [H]C([H])([H])C([H])([H])C#C* 0.000 claims description 6
- 125000000069 2-butynyl group Chemical group [H]C([H])([H])C#CC([H])([H])* 0.000 claims description 6
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 125000000592 heterocycloalkyl group Chemical group 0.000 claims description 6
- LZWQNOHZMQIFBX-UHFFFAOYSA-N lithium;2-methylpropan-2-olate Chemical compound [Li+].CC(C)(C)[O-] LZWQNOHZMQIFBX-UHFFFAOYSA-N 0.000 claims description 6
- 239000002808 molecular sieve Substances 0.000 claims description 6
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 6
- 235000002906 tartaric acid Nutrition 0.000 claims description 6
- 239000011975 tartaric acid Substances 0.000 claims description 6
- 125000000474 3-butynyl group Chemical group [H]C#CC([H])([H])C([H])([H])* 0.000 claims description 5
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 5
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 5
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 5
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 5
- 125000001624 naphthyl group Chemical group 0.000 claims description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- 125000004973 1-butenyl group Chemical group C(=CCC)* 0.000 claims description 4
- 101001053401 Arabidopsis thaliana Acid beta-fructofuranosidase 3, vacuolar Proteins 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 125000001033 ether group Chemical group 0.000 claims description 4
- 125000004366 heterocycloalkenyl group Chemical group 0.000 claims description 4
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 4
- 150000003376 silicon Chemical class 0.000 claims description 4
- 238000006467 substitution reaction Methods 0.000 claims description 4
- 125000003161 (C1-C6) alkylene group Chemical group 0.000 claims description 3
- 125000006017 1-propenyl group Chemical group 0.000 claims description 3
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 claims description 3
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 3
- 125000002541 furyl group Chemical group 0.000 claims description 3
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 claims description 3
- 125000001544 thienyl group Chemical group 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- 239000003849 aromatic solvent Substances 0.000 claims description 2
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 claims description 2
- 239000002274 desiccant Substances 0.000 claims description 2
- 238000007865 diluting Methods 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052754 neon Inorganic materials 0.000 claims description 2
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 230000006340 racemization Effects 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 6
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 3
- 150000008301 phosphite esters Chemical class 0.000 claims 2
- 229920002554 vinyl polymer Polymers 0.000 claims 2
- WZKSXHQDXQKIQJ-UHFFFAOYSA-N F[C](F)F Chemical group F[C](F)F WZKSXHQDXQKIQJ-UHFFFAOYSA-N 0.000 claims 1
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 125000004618 benzofuryl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 claims 1
- 238000012805 post-processing Methods 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 11
- 238000006555 catalytic reaction Methods 0.000 abstract description 7
- 238000001308 synthesis method Methods 0.000 abstract description 2
- 239000007858 starting material Substances 0.000 description 289
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 208
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 204
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 180
- 238000005259 measurement Methods 0.000 description 76
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 75
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 60
- QJPJQTDYNZXKQF-UHFFFAOYSA-N 4-bromoanisole Chemical compound COC1=CC=C(Br)C=C1 QJPJQTDYNZXKQF-UHFFFAOYSA-N 0.000 description 37
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 36
- 239000007788 liquid Substances 0.000 description 29
- 125000004432 carbon atom Chemical group C* 0.000 description 20
- 239000000203 mixture Substances 0.000 description 19
- 239000000243 solution Substances 0.000 description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 150000002430 hydrocarbons Chemical group 0.000 description 14
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- 238000004458 analytical method Methods 0.000 description 12
- 238000004440 column chromatography Methods 0.000 description 12
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 11
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 10
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 10
- 125000002950 monocyclic group Chemical group 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 239000002585 base Substances 0.000 description 9
- 239000003208 petroleum Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000004128 high performance liquid chromatography Methods 0.000 description 8
- 239000000741 silica gel Substances 0.000 description 8
- 229910002027 silica gel Inorganic materials 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 125000002947 alkylene group Chemical group 0.000 description 7
- 125000002619 bicyclic group Chemical group 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 150000001721 carbon Chemical group 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 229920006395 saturated elastomer Polymers 0.000 description 7
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 6
- 125000004122 cyclic group Chemical group 0.000 description 6
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical class [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 6
- 125000003367 polycyclic group Chemical group 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 125000005913 (C3-C6) cycloalkyl group Chemical group 0.000 description 5
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000012043 crude product Substances 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 125000000392 cycloalkenyl group Chemical group 0.000 description 5
- 125000000532 dioxanyl group Chemical group 0.000 description 5
- 239000012039 electrophile Substances 0.000 description 5
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 5
- 239000012044 organic layer Substances 0.000 description 5
- 239000012074 organic phase Substances 0.000 description 5
- 239000001301 oxygen Chemical group 0.000 description 5
- 239000011593 sulfur Chemical group 0.000 description 5
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 125000001047 cyclobutenyl group Chemical group C1(=CCC1)* 0.000 description 4
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 4
- 125000002433 cyclopentenyl group Chemical group C1(=CCCC1)* 0.000 description 4
- 125000000298 cyclopropenyl group Chemical group [H]C1=C([H])C1([H])* 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 125000005647 linker group Chemical group 0.000 description 4
- 125000003003 spiro group Chemical group 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- 125000006656 (C2-C4) alkenyl group Chemical group 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000003277 amino group Chemical class 0.000 description 3
- 125000001246 bromo group Chemical group Br* 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 125000003718 tetrahydrofuranyl group Chemical group 0.000 description 3
- 125000006650 (C2-C4) alkynyl group Chemical group 0.000 description 2
- WYECURVXVYPVAT-UHFFFAOYSA-N 1-(4-bromophenyl)ethanone Chemical compound CC(=O)C1=CC=C(Br)C=C1 WYECURVXVYPVAT-UHFFFAOYSA-N 0.000 description 2
- PLDWAJLZAAHOGG-UHFFFAOYSA-N 1-bromo-3-methoxybenzene Chemical compound COC1=CC=CC(Br)=C1 PLDWAJLZAAHOGG-UHFFFAOYSA-N 0.000 description 2
- AITNMTXHTIIIBB-UHFFFAOYSA-N 1-bromo-4-fluorobenzene Chemical compound FC1=CC=C(Br)C=C1 AITNMTXHTIIIBB-UHFFFAOYSA-N 0.000 description 2
- YEUYZNNBXLMFCW-UHFFFAOYSA-N 1-bromo-4-methylsulfanylbenzene Chemical compound CSC1=CC=C(Br)C=C1 YEUYZNNBXLMFCW-UHFFFAOYSA-N 0.000 description 2
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-Tetramethylpiperidine Substances CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- 125000004974 2-butenyl group Chemical group C(C=CC)* 0.000 description 2
- YYAMOMYEENPVSP-UHFFFAOYSA-N 4-[(4-sulfamoylphenyl)methyl]benzenesulfonamide Chemical compound C1=CC(S(=O)(=O)N)=CC=C1CC1=CC=C(S(N)(=O)=O)C=C1 YYAMOMYEENPVSP-UHFFFAOYSA-N 0.000 description 2
- CHIMDMPJABIKAI-UHFFFAOYSA-N 5-bromocyclopenta-1,3-diene;cyclopenta-1,3-diene;iron(2+) Chemical compound [Fe+2].C=1C=C[CH-]C=1.BrC1=CC=C[CH-]1 CHIMDMPJABIKAI-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 101001053395 Arabidopsis thaliana Acid beta-fructofuranosidase 4, vacuolar Proteins 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 238000011914 asymmetric synthesis Methods 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- 125000003636 chemical group Chemical group 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 125000004852 dihydrofuranyl group Chemical group O1C(CC=C1)* 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- BEPAFCGSDWSTEL-UHFFFAOYSA-N dimethyl malonate Chemical compound COC(=O)CC(=O)OC BEPAFCGSDWSTEL-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000012634 fragment Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 125000006574 non-aromatic ring group Chemical group 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- 125000002971 oxazolyl group Chemical group 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 125000002924 primary amino group Chemical class [H]N([H])* 0.000 description 2
- 125000006413 ring segment Chemical group 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
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- PKJBWOWQJHHAHG-UHFFFAOYSA-N 1-bromo-4-phenylbenzene Chemical compound C1=CC(Br)=CC=C1C1=CC=CC=C1 PKJBWOWQJHHAHG-UHFFFAOYSA-N 0.000 description 1
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- 125000003764 2,4-dimethylpentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
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- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 1
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- 125000005916 2-methylpentyl group Chemical group 0.000 description 1
- 125000004337 3-ethylpentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000005917 3-methylpentyl group Chemical group 0.000 description 1
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- 125000006163 5-membered heteroaryl group Chemical group 0.000 description 1
- 125000006164 6-membered heteroaryl group Chemical group 0.000 description 1
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- 125000001313 C5-C10 heteroaryl group Chemical group 0.000 description 1
- JQOATXDBTYKMEX-UHFFFAOYSA-N CC[Zn] Chemical compound CC[Zn] JQOATXDBTYKMEX-UHFFFAOYSA-N 0.000 description 1
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- 238000010499 C–H functionalization reaction Methods 0.000 description 1
- UFHFLCQGNIYNRP-VVKOMZTBSA-N Dideuterium Chemical compound [2H][2H] UFHFLCQGNIYNRP-VVKOMZTBSA-N 0.000 description 1
- 101000652482 Homo sapiens TBC1 domain family member 8 Proteins 0.000 description 1
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- 230000009471 action Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000000746 allylic group Chemical group 0.000 description 1
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 1
- 125000000732 arylene group Chemical group 0.000 description 1
- 238000007294 asymmetric addition reaction Methods 0.000 description 1
- 125000003725 azepanyl group Chemical group 0.000 description 1
- 125000002393 azetidinyl group Chemical group 0.000 description 1
- 125000004069 aziridinyl group Chemical group 0.000 description 1
- 125000000499 benzofuranyl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 150000005829 chemical entities Chemical class 0.000 description 1
- XGRJZXREYAXTGV-UHFFFAOYSA-N chlorodiphenylphosphine Chemical compound C=1C=CC=CC=1P(Cl)C1=CC=CC=C1 XGRJZXREYAXTGV-UHFFFAOYSA-N 0.000 description 1
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000003678 cyclohexadienyl group Chemical group C1(=CC=CCC1)* 0.000 description 1
- 125000006547 cyclononyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 125000002576 diazepinyl group Chemical group N1N=C(C=CC=C1)* 0.000 description 1
- 125000005879 dioxolanyl group Chemical group 0.000 description 1
- VURFVHCLMJOLKN-UHFFFAOYSA-N diphosphane Chemical compound PP VURFVHCLMJOLKN-UHFFFAOYSA-N 0.000 description 1
- 125000005883 dithianyl group Chemical group 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 125000005677 ethinylene group Chemical group [*:2]C#C[*:1] 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000003838 furazanyl group Chemical group 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 125000003707 hexyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002632 imidazolidinyl group Chemical group 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 125000000654 isopropylidene group Chemical group C(C)(C)=* 0.000 description 1
- 125000004628 isothiazolidinyl group Chemical group S1N(CCC1)* 0.000 description 1
- 125000001786 isothiazolyl group Chemical group 0.000 description 1
- 125000003965 isoxazolidinyl group Chemical group 0.000 description 1
- 125000000842 isoxazolyl group Chemical group 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000005394 methallyl group Chemical group 0.000 description 1
- 125000002757 morpholinyl group Chemical group 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001715 oxadiazolyl group Chemical group 0.000 description 1
- 125000005880 oxathiolanyl group Chemical group 0.000 description 1
- 125000000160 oxazolidinyl group Chemical group 0.000 description 1
- 125000003585 oxepinyl group Chemical group 0.000 description 1
- 125000000466 oxiranyl group Chemical group 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Chemical group 0.000 description 1
- 125000004193 piperazinyl group Chemical group 0.000 description 1
- 125000003386 piperidinyl group Chemical group 0.000 description 1
- 238000007867 post-reaction treatment Methods 0.000 description 1
- XOFYZVNMUHMLCC-ZPOLXVRWSA-N prednisone Chemical compound O=C1C=C[C@]2(C)[C@H]3C(=O)C[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 XOFYZVNMUHMLCC-ZPOLXVRWSA-N 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000003072 pyrazolidinyl group Chemical group 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 125000002098 pyridazinyl group Chemical group 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 125000000719 pyrrolidinyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 125000003410 quininyl group Chemical group 0.000 description 1
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 125000001412 tetrahydropyranyl group Chemical group 0.000 description 1
- 125000005958 tetrahydrothienyl group Chemical group 0.000 description 1
- 125000005247 tetrazinyl group Chemical group N1=NN=NC(=C1)* 0.000 description 1
- 125000003831 tetrazolyl group Chemical group 0.000 description 1
- 125000001113 thiadiazolyl group Chemical group 0.000 description 1
- 125000001984 thiazolidinyl group Chemical group 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 125000001583 thiepanyl group Chemical group 0.000 description 1
- 125000002053 thietanyl group Chemical group 0.000 description 1
- 125000001730 thiiranyl group Chemical group 0.000 description 1
- 125000004568 thiomorpholinyl group Chemical group 0.000 description 1
- 125000004306 triazinyl group Chemical group 0.000 description 1
- 125000001425 triazolyl group Chemical group 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
- C07F17/00—Metallocenes
- C07F17/02—Metallocenes of metals of Groups 8, 9 or 10 of the Periodic Table
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2282—Unsaturated compounds used as ligands
- B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
- C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
-
- 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
-
- 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
- C07B2200/13—Crystalline forms, e.g. polymorphs
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
Abstract
本发明公开了一种平面手性茂金属化合物、其合成方法及应用。本发明提供了一种平面手性茂金属化合物的制备方法，其包括以下步骤：保护气体氛围下，在有机溶剂中，在手性膦配体、铑催化剂和碱的存在下，将如式rac‑II所示消旋化合物与如式III所示化合物进行所示的芳基化反应，分别得到平面手性茂金属化合物即可。该平面手性茂金属原料可以用于进一步制备手性配体，该手性配体在不对称催化中有着广泛的应用。
Description
技术领域
本发明涉及一种平面手性茂金属化合物、其合成方法及应用。该方法可以以取代的茂金属，卤代芳环或卤代杂环芳烃为原料，手性膦配体和铑为催化剂，利用动力学拆分的策略，高效率、高选择性(高对映选择性，高区域选择性)地合成这类平面手性茂金属化合物。这类平面手性茂金属化合物能方便转化为一系列手性配体。
背景技术
平面手性化合物在药物化学，不对称催化和材料化学领域中是非常常见的骨架(Acc.Chem.Res.2000，33，412；Acc.Chem.Res.2004，37，542；Angew.Chem.Int.Ed.2006，45，7674.)。化学家们一直以来致力于发展一类高效的方法将引入平面手性。到目前为止，常用的策略是利用手性辅基或者当量的手性碱。利用上述方法可以合成多种平面手性茂金属化合物，但这些方法具有明显的局限性，如需要预装手性辅基或使用空气敏感的金属试剂。利用不对称催化的方法，尤其是不对称催化碳氢键活化的方法，可以高效快捷地合成平面手性茂金属化合物。
1，2-二取代、1，2，3-三取代和1，3-二取代二茂铁的一般合成反应方案如下(Organometallics 2007，26，3850)：
Scheme 1.General Reaction Schemes for the Synthesis of
1，2-Di-，1，2，3-Tri-，and 1，3-Disubstituted Ferrocenes route 1
route 2
上述方法仅能适用于特定基团，取代位置受限，普适性差。
另外需要强调的是，1,3-二取代平面手性茂金属化合物的合成非常具有挑战性，一般在手性导向基的作用下，使用当量碱在邻位引入溴原子，然后再次使用当量碱和亲电试剂反应，在溴的邻位引入所需官能图，最后脱除溴原子，实现手性1,3-二取代平面手性二茂铁化合物的合成(Chem.Commun.2005,4929。Organometallics 2007,26,3850)。
另外，在中国发明专利CN2019108903644中公开的内容，使用的原料II是不涉及手性的底物，其产物的手性完全由手性配体决定，其可高手性纯度的得到目标化合物，所以不存在手性拆分过程，
发明内容
本发明所要解决的技术问题是提供了一种与现有技术完全不同的手性茂金属衍生物及其制备方法和应用。本发明提供了一种新型平面手性茂金属化合物，利用易得的手性膦配体，利用动力学拆分的策略，发展了吡啶导向的不对称偶联反应，高效地合成了平面手性茂金属化合物并可回收光学纯的手性茂金属原料，并且该平面手性茂金属原料可以用于进一步制备手性配体，该手性配体在不对称催化中有着广泛的应用。
本发明提供了一种平面手性茂金属化合物的制备方法，其包括以下步骤：保护气体氛围下，在有机溶剂中，在手性膦配体、铑催化剂和碱的存在下，将如式rac-II所示消旋化合物(原料为式II和式II’所示化合物的消旋体)与如式III所示化合物进行如下所示的芳基化反应，分别得到平面手性茂金属化合物即可(如式II和/或式I、或者式II’和/或式I’所示的平面手性茂金属化合物)；
或者
其中，X独立地为卤素；
R1、R2和R3独立地为H、F、Cl、Br、I、C1-C10的烷基、C1-C10的烷基-O-、C3-C10的环烷基或苯基；
或者，R1、R2和R3中任意两个相邻的基团相连，与其所连接的碳共同形成苯基、C3-C6的脂环烃基、或C3-C5的杂脂环烃基；所述的C3-C5的杂脂环烃基中，杂原子选自N、O和S中的一种或多种，杂原子个数为1-2个；
R4和R5独立地为H、F、Cl、Br、I、C1-C10的烷基、C1-C10的烷基-O-、C3-C6的环烷基、C2-C10的烯基、C2-C10的炔基、C1-C10的烷基-S-、一个或二个C1-C10的烷基取代的胺基、三个C1-C10的烷基取代的硅基或苯基，或者，被1、2或3个Ra基团取代的：C1-C10的烷基、C1-C10的烷基-O-、C3-C6的环烷基、C2-C10的烯基、C2-C10的炔基、C1-C10的烷基-S-、一个或二个C1-C10的烷基取代的胺基、三个C1-C10的烷基取代的硅基或苯基；
所述的Ra独立地为D、F、Cl、Br、I、C1-C10的烷基、C1-C10的烷基-O-或C3-C10的环烷基；且R4和R5不同时为H；
或者，R4和R5中基团相连，与其所连接的碳共同形成苯基、C3-C6的脂环烃基或C3-C5的杂脂环烃基；所述的C3-C5的杂脂环烃基中，杂原子选自N、O和S中的一种或多种，杂原子个数为1-2个；
R6独立地为H、F、Cl、Br、I或R6a-L1-；
R6a独立地为H、未取代或被一个或多个R6a-1取代的C1-C10的脂烃基、未取代或被一个或多个R6a-2取代的C3-C10的脂环烃基、未取代或被一个或多个R6a-3取代的C6-C12的芳基、或被三个C1-C10的烷基取代的硅基；
R7独立地为未取代或被一个或多个R7-1取代的C6-C12的芳基、或未取代或被一个或多个R7-2取代的5-12元的杂芳基；所述的5-12元的杂芳基中，杂原子选自N、O和S中的一种或多种，杂原子个数为1-4个；当所述的取代基个数为多个时，相同或不同；
R7-1和R7-2独立地为F、Cl、Br、I、硝基、氰基、或R7a-L2；
或者，当R7-1和R7-2独立地为多个时，任意两个相邻基团连接，与其所连接的原子共同形成C3-C6的脂环烃基或C3-C5的杂脂环烃基；所述的C3-C5的杂脂环烃基中，杂原子选自N、O和S中的一种或多种，杂原子个数为1-2个；
L1和L2独立地为连接键、C1-C6的亚烷基、-(C1-C6的亚烷基)-O-、-O-、-S-、-C(＝O)-、-C(＝O)O-、-N(RL)-或-S(＝O)2-；
RL独立地为H或C1-C6的烷基；
R7a独立地为H、未取代或被一个或多个R7a-1取代的C1-C6的烷基、或未取代或被一个或多个R7a-2取代的苯基；
R6a-1、R6a-2、R7a-1和R7a-2独立地为F、Cl、Br、I或C1-C6的烷基；
M独立地为Fe和Ru。
本发明中，所述的平面手性茂金属化合物(如式I、式I’、如式II、式II’所示的平面手性茂金属化合物)中某些取代基的定义可如下所述，未提及的取代基的定义均如上任一方案所述。
在本发明的某一方案中，Ra、R1、R2和R3独立地为C1-C10的烷基和C1-C10的烷基-O-里的C1-C10的烷基独立地为C1-C6的烷基(例如甲基、乙基、丙基、丁基、戊基或己基)，还可为C1～C4烷基(例如甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基或叔丁基)，又例如甲基。
在本发明的某一方案中，Ra、R1、R2和R3独立地为C3-C10的环烷基里的C3-C10的环烷基(可为单环或多环环烷基)独立地为C3-C6的环烷基(例如环丙基、环丁基、环戊基或环己基)。
在本发明的某一方案中，所述的R1、R2和R3中任意两个相邻的基团相连，与其所连接的碳共同形成C3-C6的脂环烃基里的C3-C6的脂环烃基独立地为C3-C6的环烷基(例如环丙基、环丁基、环戊基或环己基)或C3-C6的环烯基(例如环丙烯基、环丁烯基、环戊烯基或环己烯基)；其与所示的吡啶环并环连接(稠合)。
在本发明的某一方案中，所述的R1、R2和R3中任意两个相邻的基团相连，与其所连接的碳共同形成C3-C5的杂脂环烃基里的C3-C5的杂脂环烃基独立地为C3-C5的杂环烷基(例如四氢呋喃基或二氧杂环己烷基)或C3-C5的杂环烯基(例如二氢呋喃基或二氧杂环己烯基)；其与所示的吡啶环并环连接(稠合)。
在本发明的某一方案中，R4和R5独立地为C1-C10的烷基、被取代的C1-C10的烷基、C1-C10的烷基-O-、被取代的C1-C10的烷基-O-、C1-C10的烷基-S-、被取代的C1-C10的烷基-S-、被一个或二个C1-C10的烷基取代的胺基、被取代的一个或二个C1-C10的烷基取代的胺基、被三个C1-C10的烷基取代的硅基、被取代的三个C1-C10的烷基取代的硅基里的C1-C10的烷基独立地为C1-C6的烷基，例如甲基、乙基、丙基、丁基、戊基或己基，还可为C1～C4烷基(例如甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基或叔丁基)，又例如甲基。所述的C1-C10的烷基-O-、被取代的C1-C10的烷基-O-里的C1-C10的烷基-O-例如甲氧基、乙氧基、丙氧基、丁氧基、戊氧基或己氧基。所述的C1-C10的烷基-S-、被取代的C1-C10的烷基-S-里的C1-C10的烷基-S-例如甲硫基、乙硫基、丙硫基、丁硫基、戊硫基或己硫基。
在本发明的某一方案中，R4和R5独立地为C2-C10的烯基、被取代的C2-C10的烯基里的C2-C10的烯基为C2-C4的烯基，例如乙烯基1-丙烯基2-丙烯基或异丙烯基烯丙基1-丁烯基2-丁烯基2-甲基烯丙基2-甲基丙-1-烯-1-基丁-3-烯-1-基或2-甲基-丙-1-烯-1-基
在本发明的某一方案中，R4和R5独立地为C2-C10的炔基、被取代的C2-C10的炔基里的C2-C10的炔基为C2-C4的炔基，例如乙炔基、丙-1-炔基、丙-2-炔基、丁-1-炔基、丁-2-炔基、丁-3-炔基或1-甲基丙-2-炔基。
在本发明的某一方案中，所述的R4和R5中任意两个相邻的基团相连，与其所连接的碳共同形成C3-C6的脂环烃基里的C3-C6的脂环烃基独立地为C3-C6的环烷基(例如环丙基、环丁基、环戊基或环己基)或C3-C6的环烯基(例如环丙烯基、环丁烯基、环戊烯基或环己烯基)。
在本发明的某一方案中，所述的R4和R5中任意两个相邻的基团相连，与其所连接的碳共同形成C3-C5的杂脂环烃基里的C3-C5的杂脂环烃基独立地为C3-C5的杂环烷基(例如四氢呋喃基或二氧杂环己烷基)或C3-C5的杂环烯基(例如二氢呋喃基或二氧杂环己烯基)。
在本发明的某一方案中，所述的未取代或被一个或多个R6a-1取代的C1-C10的脂烃基里的C1-C10的脂烃基独立地为C1-C10的烷基{又可为C1-C6的烷基(例如甲基、乙基、丙基、丁基、戊基或己基)，还可为C1～C4烷基(例如甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基或叔丁基)，又例如异丙基}、C2-C10的烯基{又可为C2-C4的烯基，例如乙烯基1-丙烯基2-丙烯基或异丙烯基烯丙基1-丁烯基2-丁烯基2-甲基烯丙基2-甲基丙-1-烯-1-基丁-3-烯-1-基较佳地为乙烯基或烯丙基又例如}、或C2-C10的炔基{又可为C2-C4的炔基，例如乙炔基、丙-1-炔基、丙-2-炔基、丁-1-炔基、丁-2-炔基、丁-3-炔基或1-甲基丙-2-炔基}。
在本发明的某一方案中，所述的未取代或被一个或多个R6a-2取代的C3-C10的脂环烃基里的C3-C10的脂环烃基独立地为C3-C10的环烷基(又可为C3-C6的环烷基，例如环丙基、环丁基、环戊基或环己基)、或C3-C10的环烯基(又可为C3-C6的环烯基，例如环丙烯基、环丁烯基、环戊烯基或环己烯基)。
在本发明的某一方案中，所述的未取代或被一个或多个R6a-3取代的C6-C12的芳基里的C6-C14的芳基独立地为苯基、茚基或萘基。
在本发明的某一方案中，所述的R6a独立地为三个C1-C10的烷基取代的硅基里的C1-C10的烷基独立地为C1-C6的烷基(例如甲基、乙基、丙基、丁基、戊基或己基)，还可为C1～C4烷基(例如甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基或叔丁基)，又例如甲基。
在本发明的某一方案中，所述的未取代或被一个或多个R7-1取代的C6-C12的芳基里的C6-C12的芳基独立地为苯基、茚基或萘基。
在本发明的某一方案中，所述的未取代或被一个或多个R7-2取代的5-12元的杂芳基里的5-12元的杂芳基中，杂原子选自N、O和S中的一种或多种，杂原子个数为1-2个；例如呋喃基(又例如)、噻吩基(又例如)、苯并呋喃基(又例如)、苯并噻吩基(又例如)、苯并吡咯基(又例如)或苯并吡啶基(又例如)。
在本发明的某一方案中，所述的被一个或多个R7-1取代的C6-C12的芳基中，R7-1的个数为1、2、3或4个；例如1或2。
在本发明的某一方案中，所述的被一个或多个R7-2取代的5-12元的杂芳基中，R7-2的个数为1、2、3或4个；例如1或2。
在本发明的某一方案中，当R7-1和R7-2独立地为多个，任意两个相邻基团连接，与其所连接的原子共同形成C3-C6的脂环烃基时，所述的C3-C6的脂环烃基独立地为环丙基、环丁基、环戊基或环己基。
在本发明的某一方案中，当R7-1和R7-2独立地为多个，任意两个相邻基团连接，与其所连接的原子共同形成C3-C5的杂脂环烃基时，所述的C3-C5的杂脂环烃基独立地为C3-C5的杂环烷基或C3-C5的杂环烯基；所述的C3-C5的杂环烷基可独立地为 所述的C3-C5的杂环烯基可独立地为
在本发明的某一方案中，L1和L2独立地为-C1-C6的亚烷基-或-(C1-C6的亚烷基)-O-里的C1-C6的亚烷基(例如亚甲基、亚乙基、亚丙基、亚丁基、亚戊基或亚己基)独立地为C1～C3亚烷基{亚甲基(-CH2-)，亚乙基(例如-CH2CH2-或-CH(CH3)-)，亚异丙基(例如-CH(CH3)CH2-或-C(CH3)2-)}，又例如亚甲基。
在本发明的某一方案中，RL独立地为C1-C6的烷基里的C1-C6的烷基(例如甲基、乙基、丙基、丁基、戊基或己基)独立地为C1～C4烷基(例如甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基或叔丁基)，又例如甲基。
在本发明的某一方案中，R7a独立地为未取代或被一个或多个R7a-1取代的C1-C6的烷基里的C1-C6的烷基(例如甲基、乙基、丙基、丁基、戊基或己基)为C1～C4烷基(例如甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基或叔丁基)，又例如甲基。
在本发明的某一方案中，所述的R7a-1取代的个数为1、2、3或4个。
在本发明的某一方案中，R6a-1、R6a-2、R7a-1和R7a-2独立地为C1-C6的烷基里的C1-C6的烷基(例如甲基、乙基、丙基、丁基、戊基或己基)独立地为C1～C4烷基(例如甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基或叔丁基)，又例如甲基。
在本发明的某一方案中，X为F、Cl、Br或I；例如Cl或Br。
在本发明的某一方案中，R1、R2和R3独立地为H、Me、苯基、MeO-或F。
在本发明的某一方案中，R1、R2和R3中任意两个相邻的基团相连，与其所连接的碳共同形成苯基。
在本发明的某一方案中，R4和R5独立地为H、Me、Et、nBu、CD3、Bn、 TMS、Et3Si、tBuS、F、
在本发明的某一方案中，R4为H。
在本发明的某一方案中，R4不为H。
在本发明的某一方案中，R6独立地为H、Me、nBu或iPr。
在本发明的某一方案中，R7a独立地为未取代或被一个或多个R7a-1取代的C1-C6的烷基中，所述的被多个R7a-1取代的C1-C6的烷基为三氟甲基。
在本发明的某一方案中，R7a独立地为未取代或被一个或多个R7a-2取代的苯基中，被一个R7a-2取代的苯基为对甲苯基。
在本发明的某一方案中，R7-1和R7-2独立地为F、Cl、Br、I、氰基、三氟甲基、甲基、甲基-O-、甲基-S-、苯基、-C(＝O)-CH3、-N(CH3)2、苯基或对甲苯磺酰基(Ts-)。
在本发明的某一方案中，R7独立地为
在本发明的某一方案中，独立地为
在本发明的某一方案中，独立地为
在本发明的某一方案中，所述的如式I、式I’、式II、式II’所示的茂金属化合物分别选自以下任一结构：
本发明中，所述的保护气体可为本领域常规的保护气体，例如氦气、氖气、氮气和氩气中的一种或多种，又例如氩气。
本发明中，所述的有机溶剂可为本领域常规的有机溶剂，较佳地为醚类溶剂(例如1,4-二氧六环和/或四氢呋喃)和/或芳烃类溶剂(例如甲苯)。
本发明中，所述的如式rac-II所示化合物在所述的有机溶剂中的摩尔浓度可为本领域常规的摩尔浓度，例如0.01-0.5mol/L，更佳地为0.1-0.5mol/L，进一步更佳地为0.1-0.2mol/L(例如2/15mol/L)。
本发明中，所述的铑催化剂可为本领域常规的铑催化剂，例如[Rh(C2H4)2Cl]2、[Rh(CO)2Cl]2和[Rh(cod)Cl]2中的一种或多种，又例如[Rh(C2H4)2Cl]2。
本发明中，所述的铑催化剂与所述的如式rac-II所示化合物的摩尔比可为本领域常规的摩尔比，例如0.001-0.2:1，更佳地为0.05-0.2:1，进一步更佳地为0.005-0.07:1(例如0.05:1)。
本发明中，所述的碱可为本领域常规的碱，较佳地为叔丁醇锂、叔丁醇钠、碳酸钾和碳酸铯中的一种或多种，更佳地为叔丁醇锂。
本发明中，所述的碱与所述的如式rac-II所示化合物的摩尔比可为本领域常规的摩尔比，例如1-5:1，更佳地为2-4:1(例如3:1)。
本发明中，所述的芳基化反应的温度可为本领域常规的温度，例如0-100℃，更佳地为50-70℃(例如60℃)。
本发明某一实施方案中，其中还可加入干燥剂，例如干燥的分子筛。
本发明中，所述的手性膦配体与所述的如式rac-II所示化合物的摩尔比可为本领域常规的摩尔比，较佳地为0.02-0.3:1(例如0.05:1、0.1:1、0.15:1、0.2:1或0.3:1)，更佳地为0.02-0.2:1，进一步更佳地为0.1-0.2:1(例如0.15:1)。
本发明中，所述的手性膦配体可为本领域常规的手性膦配体，例如手性双膦配体和/或手性单膦配体，例如酒石酸(taddol)衍生的亚磷酸酯配体、 或其非对映异构体
更佳地为进一步更佳地为其中，R8和R8’独立地为未取代或被一个或多个R8-1取代的C6-C10的芳基(例如苯基、萘基)，R9和R9’独立地为NR9-1R9-2或者未取代或被一个或多个R9-3取代的C6-C10的芳基(所述的C6-C10的芳基例如苯基)，R8-1和R9-3独立地为三氟甲基、C1-C4的烷基(例如甲基、乙基、丙基或异丙基)或C1-C4的烷基-O-(例如甲氧基、乙氧基、丙氧基或异丙氧基)，R9-1和R9-2独立地为C1-C4的烷基(例如甲基、乙基、丙基或异丙基)。
本发明中，所述的手性膦配体较佳地为或其非对应异构体(未定义的基团如前任一方案所述)，其中，R8为未取代或R8-1取代的C6-C10的芳基，R9为未取代或R9-3取代的C6-C10的芳基，R9-3为三氟甲基、C1-C4的烷基或C1-C4的烷基-O-。
本发明中，所述的手性膦配体较佳地为以下任一结构：
本发明中，所述的手性膦配体较佳地为或其非对应异构体。
本发明中，所述的芳基化反应的进程可采用本领域中的常规测试方法(如TLC、HPLC、GC或NMR)进行监控，一般以所述的如式rac-II所示化合物不再反应时作为反应终点。
本发明某一实施方案中，其包括如下步骤：保护气体氛围下，在有机溶剂中，在手性膦配体、铑催化剂、碱和分子筛的存在下，所述的如式rac-II所示化合物与如式III所示化合物进行芳基化反应。
本发明某一实施方案中(未定义的基团如前任一方案所述)，保护气体氛围下，在有机溶剂中，在手性膦配体、铑催化剂和碱的存在下，所述的如式rac-II所示化合物与如式III所示化合物进行芳基化反应；所述的有机溶剂为醚类溶剂；所述的手性膦配体为所述的铑催化剂为[Rh(C2H4)2Cl]2、[Rh(CO)2Cl]2和[Rh(cod)Cl]2中的一种或多种；所述的碱为叔丁醇锂、叔丁醇钠、碳酸钾和碳酸铯中的一种或多种；其中，R8为未取代或R8-1取代的C6-C10的芳基，R9为未取代或R9-3取代的C6-C10的芳基，R9-3为三氟甲基、C1-C4的烷基或C1-C4的烷基-O-。
本发明某一实施方案中(未定义的基团如前任一方案所述)，保护气体氛围下，在有机溶剂中，在手性膦配体、铑催化剂、碱和分子筛的存在下，所述的如式rac-II所示化合物与如式III所示化合物进行芳基化反应；所述的有机溶剂为醚类溶剂；所述的手性膦配体为所述的铑催化剂为[Rh(C2H4)2Cl]2、[Rh(CO)2Cl]2和[Rh(cod)Cl]2中的一种或多种；所述的碱为叔丁醇锂、叔丁醇钠、碳酸钾和碳酸铯中的一种或多种；所述的如式rac-II所示化合物在所述的有机溶剂中的摩尔浓度比为0.01-0.5mol/L；所述的手性膦配体与所述的如式rac-II所示化合物的摩尔比为0.02-0.3:1；所述的铑催化剂与所述的如式rac-II所示化合物的摩尔比为0.01-0.2:1；所述的碱与所述的如式rac-II所示化合物的摩尔比为1-5:1；所述的分子筛与所述的如式rac-II所示化合物的质量摩尔比为250-500mg/mmol；其中，R8为未取代或R8-1取代的C6-C10的芳基，R9为未取代或R9-3取代的C6-C10的芳基，R9-3为三氟甲基、C1-C4的烷基或C1-C4的烷基-O-。
本发明某一实施方案中(未定义的基团如前任一方案所述)，保护气体氛围下，在有机溶剂中，在手性膦配体、铑催化剂、碱和分子筛的存在下，所述的如式rac-II所示化合物与如式III所示化合物进行芳基化反应；所述的有机溶剂为醚类溶剂；所述的手性膦配体为所述的铑催化剂为[Rh(C2H4)2Cl]2、[Rh(CO)2Cl]2和[Rh(cod)Cl]2中的一种或多种；所述的碱为叔丁醇锂、叔丁醇钠、碳酸钾和碳酸铯中的一种或多种；所述的如式rac-II所示化合物在所述的有机溶剂中的摩尔浓度为0.1-0.2mol/L；所述的手性膦配体与所述的如式rac-II所示化合物的摩尔比为0.1-0.2:1；所述的铑催化剂与所述的如式rac-II所示化合物的摩尔比为0.05-0.07:1；所述的碱与所述的如式rac-II所示化合物的摩尔比为2-4:1；其中，R8为未取代或R8-1取代的C6-C10的芳基，R9为未取代或R9-3取代的C6-C10的芳基，R9-3为三氟甲基、C1-C4的烷基或C1-C4的烷基-O-。
本发明中，所述的芳基化反应结束后，较佳地，其还可进一步包括后处理操作。所述的后处理的操作和方法可为本领域该类反应后处理常规的操作和方法，较佳地其包括以下步骤：稀释，分离提纯。所述的稀释的操作和方法可为本领域该类反应常规的操作和方法，所述的稀释用的溶剂较佳地为乙酸乙酯。所述的分离提纯的操作和方法可为本领域常规的分离提纯的操作和方法，较佳地为柱层析分离，所述的柱层析分离的展开剂体系可为本领域该类反应常规的展开剂体系，较佳地为酯类溶剂/醚类溶剂(例如乙酸乙酯/石油醚)，更佳地为酯类溶剂/醚类溶剂＝1/20。
本发明某一实施方案中，当所述的手性膦配体选自下列化合物中的任一种时，制备得到如式II和/或式I所示的手性茂金属化合物；
本发明某一实施方案中，当所述的手性膦配体选自下列化合物中的任一种时，制备得到如式II’和/或式I’所示的手性茂金属化合物；
本发明还提供了一种如式I、式I’、式II、式II’所示化合物，其结构如下所示，
其中，M、R1、R2、R3、R4、R5、R6和R7的定义如前任一项所述。
本发明还提供了一种平面手性吡啶类二茂金属化合物，其结构如式VI-1、VI-2、VI-3或式VI-4所示，
其中，M、R1、R2、R3、R4、R5和R6的定义如前任一项所述，R10独立地为：卤素、
Ar1、Ar2和Ar3独立地为
R10-1、R10-2、R10-3、R10-4和R10-5独立地为H、F、Cl、Br、I、CF3；
L4独立地为连接键、亚乙炔基；
R10a、R10b、R10c、R11a、R11b和R11c独立地为C1-C6的烷基。
本发明中，所述的平面手性吡啶类二茂金属化合物中某些取代基的定义可如下所述，未提及的取代基的定义均如上任一方案所述。
在本发明的某一方案中，所述的卤素独立地为F、Cl、Br或I，例如Cl或Br。
在本发明的某一方案中，R10a、R10b、R10c、R11a、R11b和R11c独立地为C1-C6的烷基里的C1-C6的烷基(例如甲基、乙基、丙基、丁基、戊基或己基)独立地为C1～C4烷基(例如甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基或叔丁基)，又例如甲基。
在本发明的某一方案中，Ar1、Ar2和Ar3独立地为苯基。
在本发明的某一方案中，独立地为三甲基硅烷基(TMS)或三异丙基硅炔基(TIPS)。
在本发明的某一方案中，所述的平面手性吡啶类二茂铁化合物中，所述的如式VI所示的平面手性吡啶类二茂铁化合物选自如下结构：
VI-3为
所述的平面手性吡啶类二茂金属化合物可采用本领域常规的方法制备得到，例如使用所述的平面手性茂金属化合物。
本发明还提供了一种如上所述的如式VI-1、VI-2、VI-3或式VI-4所示的平面手性吡啶类二茂金属化合物在不对称合成中的应用；较佳地其在不对称乙基锌对醛的不对称加成反应和烯丙基取代反应中作为手性配体催化剂。
基团定义
除非另外说明，应当应用本文所使用的下列定义。出于本发明的目的，化学元素与元素周期表CAS版，和《化学和物理手册》，第75版，1994一致。此外，有机化学一般原理可参考"Organic Chemistry",Thomas Sorrell,University Science Books,Sausalito:1999,和"March's Advanced Organic Chemistry”by Michael B.Smith and Jerry March,JohnWiley&Sons,New York:2007中的描述，其全部内容通过引用并入本文。
在本说明书中，可由本领域技术人员选择基团及其取代基以提供稳定的结构部分和化合物。当通过从左向右书写的常规化学式描述取代基时，该取代基也同样包括从右向左书写结构式时所得到的在化学上等同的取代基。
在本文中定义的某些化学基团前面通过简化符号来表示该基团中存在的碳原子总数。例如，C1-C6烷基是指具有总共1、2、3、4、5或6个碳原子的如下文所定义的烷基。简化符号中的碳原子总数不包括可能存在于所述基团的取代基中的碳。
在本文中，取代基中定义的数值范围如0至4、1-4、1至3等表明该范围内的整数，如1-6为1、2、3、4、5、6。
除前述以外，当用于本申请的说明书及权利要求书中时，除非另外特别指明，否则以下术语具有如下所示的含义。
术语“包括”为开放式表达，即包括本发明所指明的内容，但并不排除其他方面的内容。
术语“被取代的”是指特定原子上的任意一个或多个氢原子被取代基取代，包括重氢和氢的变体，只要特定原子的价态是正常的并且取代后的化合物是稳定的。
一般而言，术语“取代的”表示所给结构中的一个或多个氢原子被具体取代基所取代。进一步地，当该基团被1个以上所述取代基取代时，所述取代基之间是相互独立，即，所述的1个以上的取代基可以是互不相同的，也可以是相同的。除非其他方面表明，一个取代基团可以在被取代基团的各个可取代的位置进行取代。当所给出的结构式中不只一个位置能被选自具体基团的一个或多个取代基所取代，那么取代基可以相同或不同地在各个位置取代。
在本说明书的各部分，本发明公开化合物的取代基按照基团种类或范围公开。特别指出，本发明包括这些基团种类和范围的各个成员的每一个独立的次级组合。例如，术语“C1～C6烷基”或“C1-6烷基”特别指独立公开的甲基、乙基、C3烷基、C4烷基、C5烷基和C6烷基；“C1-4烷基”特指独立公开的甲基、乙基、C3烷基(即丙基，包括正丙基和异丙基)、C4烷基(即丁基，包括正丁基、异丁基、仲丁基和叔丁基)。
术语“卤素”选自于F，Cl，Br或I，尤其指F或Cl。
在本申请中，除非另有规定，作为基团或是其它基团的一部分，术语“脂烃基”或“脂肪烃基”或者其下位概念(还可以再分成“烷基”(alkyl；通式是CnH2n+1)、“烯基”(alkenyl)、“炔基”(alkynyl))本身或者作为另一取代基的一部分表示直链的或支链的烃原子团或其组合，可以是完全饱和的、部分不饱和的、且非芳香性的，可以是单取代、二取代或多取代的，可以是一价基(如甲基)、二价基(亚…基，如亚甲基)或者多价基(次…基，如次甲基)，可以包括二价或多价原子团，具有指定数量的碳原子(如C1-C10表示1至10个碳)。
术语“饱和的”是指不包含双键或三键，即，包含全部单键的类群。
术语“部分不饱和的”是指包括至少一个双键或三键的类群。“部分不饱和的”环系统意在进一步涵盖具有多个不饱和的位点的环，但是如在此定义的不意在包括芳香族基团(例如，芳基或杂芳基基团)。
在本申请中，作为基团或是其它基团的一部分(例如用在卤素取代的烷基等基团中)，术语“烷基”意指包括具有指定碳原子数目的支链和直链的饱和脂族烃基；例如，C1-C10的烷基。如在“C1～C6烷基”中定义为包括在直链或者支链结构中具有1、2、3、4、5、或者6个碳原子的基团。其中，丙基为C3烷基(包括同分异构体，例如正丙基或异丙基)；丁基为C4烷基(包括同分异构体，例如正丁基、仲丁基、异丁基或叔丁基)；戊基为C5烷基(包括同分异构体，例如正戊基、1-甲基-丁基、1-乙基-丙基、2-甲基-1-丁基、3-甲基-1-丁基、异戊基、叔戊基或新戊基)；己基为C6烷基(包括同分异构体，例如正己基、1-乙基-2-甲基丙基、1，1，2-三甲基丙基、1，1-二甲基丁基、1，2-二甲基丁基、2，2-二甲基丁基、1，3-二甲基丁基、2-乙基丁基、2-甲基戊基、3-甲基戊基、4-甲基戊基、2，3-二甲基丁基)。此外，庚基为C7烷基(包括同分异构体，例如正庚基、2，4-二甲基戊基、2，2-二甲基戊基、3，3-二甲基戊基、2-乙基戊基、3-乙基戊基)。辛基为C8烷基(包括同分异构体，例如正辛基、2，3-二甲基己基、2，4-二甲基己基、2，5-二甲基己基、2，2-二甲基己基、3，3-二甲基己基、4，4-二甲基己基、2-乙基己基、3-乙基己基、4-乙基己基、2-甲基-2-乙基戊基、2-甲基-3-乙基戊基)。壬基为C9烷基(包括同分异构体，例如正壬基、2-甲基-2-乙基己基、2-甲基-3-乙基己基、2，2-二乙基戊基)。奎基为C10烷基(包括同分异构体，例如正奎基、3，3-二乙基己基、2，2-二乙基己基)。在某一实施方案中，所述的“烷基”优选含有1至6个碳原子的直链或支链的烷基。在某一实施方案中，所述的“烷基”是指C1-C6烷基。在某一实施方案中，所述的“烷基”是指C1-C4烷基。
在本申请中，作为基团或是其它基团的一部分，术语“烯基”意指仅由碳原子和氢原子组成、含有至少一个碳碳双键、并且没有碳碳三键的具有例如2-10个(例如为2-6个，优选为2-4个)碳原子且通过单键与分子的其余部分连接的直链或支链的烃链基团。该一个或多个碳碳双键可以是内部的(例如在2-丁烯基中)或末端的(例如在1-丁烯基中)。在一些实施例中，烯基基团具有2至4个碳原子(“C2-C4的烯基”)。优选存在一个碳碳双键。C2-C4的烯基的实例包括乙烯基(C2；)、1-丙烯基(C3；)、2-丙烯基或异丙烯基(C3；)、烯丙基(C3；)、1-丁烯基(C4；)、2-丁烯基(C4 )(巴豆基)、2-甲基烯丙基(C4；)、2-甲基丙-1-烯-1-基(C4；)、丁-3-烯-1-基(C4；)、丁二烯基{C4；例如(E)-丁-1,3-二烯-1-基苯}，以及异构体(例如顺反异构体或立体异构体)。在一些实施例中，烯基基团为以及异构体(例如顺反异构体或立体异构体)。
在本申请中，作为基团或是其它基团的一部分，术语“炔基”意指仅由碳原子和氢原子组成、含有至少一个碳碳三键的具有例如2-10个(例如为2-6个，优选为2-4个)碳原子且通过单键与分子的其余部分连接的直链或支链的烃链基团。该一个或多个碳碳三键可以是内部的(例如在2-丁炔基中)或末端的(例如在1-丁炔基中)。在一些实施例中，炔基基团具有2至4个碳原子(“C2-C4炔基”)，例如乙炔基(C2)、丙-1-炔基(C3)、丙-2-炔基(C3)、丁-1-炔基(C4)、丁-2-炔基(C4)、丁-3-炔基(C4)或1-甲基丙-2-炔基(C4)。
在本申请中，作为基团或是其它基团的一部分，术语“脂环烃基”意指仅由碳原子和氢原子组成的稳定的非芳香族单环(“单环的脂环烃基”)或多环脂烃基(例如二环系统(“二环的脂环烃基”))，其可包括稠合环体系、桥环体系或螺环体系，且其为饱和或部分不饱和并可经由任何适宜的碳原子通过单键与分子的其余部分连接。例如，环烷基、环烯基。在一些实施例中，脂环烃基具有3-10个碳原子的环可以表示为C3-C10脂环烃基。在一些实施例中，脂环烃基具有3-6个碳原子的环可以表示为C3-C6脂环烃基。
在本申请中，作为基团或是其它基团的一部分，除非另有规定，术语“环烷基”意指仅由碳原子和氢原子组成的饱和的单环、多环或者桥接碳环取代基，且其可经由任何适宜的碳原子通过单键与分子的其余部分连接；当为多环时，可为并环连接或螺环连接(即，碳原子上的两个偕氢被亚烷基取代)的桥环体系或螺环体系。环烷基取代基可以经任何适宜的碳原子连接在中心分子上。在一些实施例中，具有3-10个碳原子的环可以表示为C3-C16环烷基。在一些实施例中，C3～C6的环烷基包括环丙基(C3)、环丁基(C4)、环戊基(C5)及环己基(C6)。在一些实施例中，C3～C10的环烷基的实例包括上述C3～C6环烷基基团连同环庚基(C7)、环辛基(C8)、环壬基(C9)及环癸基(C10)。
在本申请中，本身或者作为另一取代基的一部分，术语“环烯基”是指含有部分不饱和双键的单环、多环或者桥接碳环取代基，且其可经由任何适宜的碳原子通过单键与分子的其余部分连接；当为多环时，可为并环连接或螺环连接(即，碳原子上的两个偕氢被亚烷基取代)的桥环体系或螺环体系。在一些实施例中，“环烯基”是具有3至10个环原子的单环的，不饱和的碳环烯基基团(“C3-C16环烯基”)。示例性C3-C6碳环烯基基团包括但不限于，环丙烯基(C3)、环丁烯基(C4)、环戊烯基(C5 )、环戊二烯(C5 )、环己烯基(例如)或环己二烯基，以及其立体异构体。
除非另有规定，术语“杂脂环烃基”是指具有环碳原子以及1至4个环杂原子(其中每个杂原子独立地选自氮、氧、硫、硼、磷以及硅)的非芳香族环系统的基团(例如“3-10元脂杂环基”、“C3-C5的杂脂环烃基”)。除非本说明书中另外特别指明，否则杂脂环烃基基团可以是单环的(“单环的杂脂环烃基”)或者是双环、三环或更多环的环体系，其可包括融合的、桥联的或螺的环系统(例如二环系统(“二环的杂脂环烃基”))，脂杂环基二环的环系统可以在一个或两个环中包括一个或多个杂原子)；并且可以是饱和的或可以是部分不饱和的。在一些实施例中，杂脂环烃基基团是具有碳原子以及1-4个杂原子(其中每个杂原子独立地选自氮，氧，以及硫)的稳定的3-8元非芳香族环系统(“3-6元杂脂环烃基”)，包括饱和或部分不饱和单环、双环、桥环或螺环杂环基团。优选为包含1-3个选自氮、氧和硫的杂原子的稳定的4元至6元非芳香性单环、双环、桥环或螺环基团。在一些实施例中，杂环基基团是5～6元单杂环基或稠杂环基(稠杂环基是由两个或多个单杂环基稠并而成的)。例如，杂环烷基、杂环烯基。
在本申请中，作为基团或是其它基团的一部分，术语“杂环烷基”意指由2-6个碳原子(优选3-5个碳原子)以及1-4个选自氮、氧和硫的杂原子组成的稳定的3元至7元饱和环状基团。示例性3-元杂环基基团包括但不限于，氮杂环丙基、环氧乙烷基以及硫杂环丙烷基，或者其立体异构体；示例性4-元杂环基基团包括但不限于，氮杂环丁烷基，环氧丙烷基，硫杂环丁烷基，或者其同分异构体和立体异构体；示例性5-元杂环基基团包括但不限于，四氢呋喃基，四氢噻吩基，吡咯烷基，噻唑烷基，异噻唑烷基，噁唑烷基，异噁唑烷基，咪唑烷基，吡唑烷基，二氧戊环基，氧杂硫呋喃基，二硫呋喃基，或者其同分异构体和立体异构体。示例性6-元杂环基基团包括但不限于，哌啶基，四氢吡喃基，硫化环戊烷基，吗啉基，硫代吗啉基，二噻烷基，二噁烷基，哌嗪基，三嗪烷基，或者其同分异构体和立体异构体；示例性7-元杂环基基团包括但不限于，氮杂环庚烷基，氧杂环庚烷基，硫杂环庚烷基，以及二氮杂环庚基，或者其同分异构体和立体异构体。在某一方案中，“杂环烷基”为C3～C5杂环烷基，其中杂原子选自N、O和S中的一种或多种，杂原子数为1、2或3个。
在本申请中，作为基团或是其它基团的一部分，术语“芳基”是指具有6-14个环原子以及提供在芳香族环系统中的零个杂原子单环的或多环的(例如，二环的或三环的)4n+2芳香族环系统(例如，在循环阵列中具有6，10，或14个共享的p电子)的基团(“C6-C14芳基”)。上述芳基单元的实例包括苯基、萘基、菲基、或者蒽基。在一些实施例中，为C6-C12芳基.
在本申请中，作为基团或是其它基团的一部分，术语“杂芳基”是指具有碳原子以及提供在该芳香族环系统中的1-3个杂原子(其中每个杂原子独立地选自氮、氧以及硫)的4-10元单环的或二环的4n+2芳香族环系统(例如，在循环阵列中具有6或10个共享的p电子)的基团(“4-10元杂芳基”)。在包含一个或多个氮原子的杂芳基基团中，连接点可以是碳或氮原子，只要化合价允许。在一些实施例中，所述的杂芳基为杂原子选自N、O和S中的一种或多种，杂原子数为1-4个的5-10元杂芳基。在一些实施例中，所述的杂芳基为杂原子选自N、O和S中的一种或多种，杂原子数为1～3个的4-6元杂芳基，较佳地为5-6元杂芳基。示例性5-元杂芳基基团包括但不限于：吡咯基、呋喃基、噻吩基、咪唑基、吡唑基、噁唑基、异噁唑基、噻唑基、异噻唑基、三氮唑基、噁二唑基、噻二唑基、呋咱基、噁三唑基或四唑基。示例性6-元杂芳基基团包括但不限于：吡啶基、吡嗪基、哒嗪基、嘧啶基、三嗪基或四嗪基。
本文所用术语“部分”、“结构部分”、“化学部分”、“基团”、“化学基团”是指分子中的特定片段或官能团。化学部分通常被认为是嵌入或附加到分子上的化学实体。
当所列举的取代基中没有指明其通过哪一个原子连接到化学结构通式中包括但未具体提及的化合物时，这种取代基可以通过其任何原子相键合。取代基和/或其变体的组合只有在这样的组合会产生稳定的化合物的情况下才是被允许的。
当所列举的基团中没有明确指明其具有取代基时，这种基团仅指未被取代。例如当“C1～C4烷基”前没有“取代或未取代的”的限定时，仅指“C1～C4烷基”本身或“未取代的C1～C4烷基”。
在本发明的各部分，描述了连接取代基。当该结构清楚地需要连接基团时，针对该基团所列举的马库什变量应理解为连接基团。例如，如果该结构需要连接基团并且针对该变量的马库什基团定义列举了“烷基”或“芳基”，则应该理解，该“烷基”或“芳基”分别代表连接的亚烷基基团或亚芳基基团。
在一些具体的结构中，当烷基基团清楚地表示为连接基团时，则该烷基基团代表连接的亚烷基基团，例如，基团“卤代-C1～C6烷基”中的C1-C6烷基应当理解为C1～C6亚烷基。
术语“亚烷基”表示从饱和的直链或支链烃基中去掉两个氢原子所得到的饱和的二价烃基基团。亚烷基基团的实例包括亚甲基(-CH2-)，亚乙基{包括-CH2CH2-或-CH(CH3)-}，亚异丙基{包括-CH(CH3)CH2-或-C(CH3)2-}等等。
除非另有规定，本文使用的所有技术术语和科学术语具有要求保护主题所属领域的标准含义。倘若对于某术语存在多个定义，则以本文定义为准。
应该理解，在本发明中使用的单数形式，如“一种”，包括复数指代，除非另有规定。此外，术语“包括”是开放性限定并非封闭式，即包括本发明所指明的内容，但并不排除其他方面的内容。
除非另有说明，本发明采用质谱、元素分析的传统方法，各步骤和条件可参照本领域常规的操作步骤和条件。
除非另有指明，本发明采用分析化学、有机合成化学和光学的标准命名及标准实验室步骤和技术。在某些情况下，标准技术被用于化学合成、化学分析、发光器件性能检测。
另外，需要说明的是，除非以其他方式明确指出，在本发明中所采用的描述方式“…独立地为”应做广义理解，是指所描述的各个个体之间是相互独立的，可以独立地为相同或不同的具体基团。更详细地，描述方式“…独立地为”既可以是指在不同基团中，相同符号之间所表达的具体选项之间互相不影响；也可以表示在相同的基团中，相同符号之间所表达的具体选项之间互相不影响。
本领域技术人员可以理解，根据本领域中使用的惯例，本申请描述基团的结构式中所使用的是指，相应的基团通过该位点与化合物中的其它片段、基团进行连接。
在不违背本领域常识的基础上，上述各优选条件，可任意组合，即得本发明各较佳实例。
本发明所用试剂和原料均市售可得。
本发明的积极进步效果在于：本发明提出了一种平面手性的茂金属化合物的制备方法。利用该制备方法可以合成单一构型的茂金属化合物，具有底物普适性较好、高对映选择性、高反应收率以及高反应效率等优势。该平面手性茂金属原料可以用于进一步制备手性配体，在不对称催化中开发出更广泛的应用。
具体实施方式
下面通过实施例的方式进一步说明本发明，但并不因此将本发明限制在所述的实施例范围之中。下列实施例中未注明具体条件的实验方法，按照常规方法和条件，或按照商品说明书选择。
下述实施例中，室温是指10-30℃。t(major)表示主产物的出峰时间,t(minor)表示副产物(对映异构体)的出峰时间。eeSM是指反应结束后分离得到的手性原料的ee值。eePR是指反应结束后分离得到的手性产物的ee值。
实施例1：平面手性茂金属化合物I和II的不对称合成
为的消旋体。
在完全干燥的10mL Schlenk管中加入LiOtBu(48.0mg,0.6mmol)、(R,R)-P6(25.3mg,0.04mmol)、[Rh(C2H4)2Cl]2(3.9mg,0.01mmol)、rac-II(0.2mmol,1.0equiv)和卤代芳烃III(0.4mmol,2.0equiv)。将体系抽换氩气三次，然后加入四氢呋喃(2.0mL)。加热至60℃反应8-23小时，过滤，减压除去溶剂，柱层析纯化(石油醚/乙酸乙酯＝20/1,v/v)。
以下实施例2-实施例60的化合物参照实施例1制备获得。
实施例2
卤代芳烃III为对甲氧基溴苯，34.4mg,45％yield,96％ee.分析数据:[α]D 27＝+259.9(c＝0.1丙酮).1H NMR(400MHz,CD2Cl2)δ8.56(ddd,J＝5.2,2.0,1.2Hz,1H),7.56(td,J＝8.0,2.0Hz,1H),7.46(dt,J＝8.0,1.2Hz,1H),7.17-7.13(m,3H),6.71(d,J＝8.8Hz,2H),4.43(d,J＝2.4Hz,1H),4.35(d,J＝2.4Hz,1H),4.08(s,5H),3.77(s,3H),2.12(s,3H).13C NMR(101MHz,CD2Cl2)δ158.9,158.8,149.5,135.7,131.24,131.17,127.7,121.6,113.8,88.4,86.7,85.5,72.4,70.0,68.5,55.9,14.9.IR(薄膜):νmax(cm-1)＝2986,2902,1609,1585,1561,1518,1481,1455,1430,1409,1377,1300,1274,1243,1175,1148,1104,1076,1034,912,892,814,787,744,701,638,611.HRMS(ESI)计算值C23H22[56Fe]NO[M+H]+:384.1045.实测值:384.1046.手性柱Daicel Chiralcel OD-H(4.6×250mm),正己烷/异丙醇＝95/05,0.7mL/min,λ＝286nm,t(minor)＝10.99min,t(major)＝11.55min.
24.8mg,45％yield,97％ee.分析数据:[α]D 29＝-89.7(c＝0.1丙酮).1H NMR(400MHz,CD2Cl2)δ8.51(d,J＝5.6Hz,1H),7.62(td,J＝7.6,1.6Hz,1H),7.59-7.55(m,1H),7.10(ddd,J＝6.8,5.2,1.2Hz,1H),4.69-4.67(m,1H),4.29(m,1H),4.22(t,J＝2.8Hz,1H),4.01(s,5H),2.34(s,3H).13C NMR(101MHz,CD2Cl2)δ160.9,149.6,136.3,123.0,121.1,84.29,84.25,72.9,71.0,69.8,67.8,16.0.IR(薄膜):νmax(cm-1)＝2972,2916,1584,1562,1488,1449,1413,1376,1289,1264,1216,1150,1103,1066,1041,1000,955,880,813,785,740,708,645,618.HRMS(ESI)计算值C16H16[56Fe]N[M+H]+:278.0627.实测值:278.0636.手性柱Daicel Chiralcel OD-H(4.6×250mm),正己烷/异丙醇＝90/10,1.0mL/min,λ＝286nm,t(minor)＝8.31min,t(major)＝12.31min.
eeSM＝96.70％；eePR＝96.46％；Calculated conversion,C＝eeSM/(eeSM+eePR)＝50％；Selectivity(s)＝ln[(1-C)(1-eeSM)]/ln[(1-C)(1+eeSM)]＝230.
实施例3
卤代芳烃III为对甲氧基溴苯，33.2mg,43％yield,93％ee.分析数据:[α]D 29＝+69.7(c＝0.1丙酮).1H NMR(400MHz,CDCl3)δ8.59(ddd,J＝4.8,2.0,0.8Hz,1H),7.51(td,J＝7.6,2.0Hz,1H),7.42(dt,J＝8.0,1.2Hz,1H),7.16(d,J＝8.8Hz,2H),7.12(ddd,J＝7.2,4.8,1.2Hz,1H),6.72(d,J＝8.8Hz,2H),4.42(d,J＝2.4Hz,1H),4.33(d,J＝2.4Hz,1H),4.08(s,5H),3.78(s,3H).13C NMR(101MHz,CDCl3)δ158.2,157.9,148.7,134.8,130.5,130.4,126.9,120.8,113.1,87.8,85.6,84.5,71.5,69.3,68.0,55.2.IR(薄膜):νmax(cm-1)＝2990,2921,2834,1609,1585,1562,1518,1480,1455,1431,1337,1301,1281,1242,1175,1151,1104,1075,1031,1000,965,930,909,812,784,745,701,674,635,619,603.HRMS(ESI)计算值C23H19[56Fe]NOD3[M+H]+:387.1234.实测值:387.1231.手性柱DaicelChiralcel OD-H(4.6×250mm),正己烷/异丙醇＝70/30,0.7mL/min,λ＝254nm,t(minor)＝8.09min,t(major)＝9.36min.
34.5mg,46％yield,99％ee.分析数据:[α]D 29＝-137.3(c＝0.1丙酮).1H NMR(400MHz,CDCl3)δ8.56-8.53(m,1H),7.63-7.54(m,2H),7.09(ddd,J＝6.4,4.8,1.2Hz,1H),4.70(s,1H),4.28(s,1H),4.22(s,1H),4.03(s,5H).13C NMR(101MHz,CDCl3)δ160.0,148.9,135.5,122.2,120.3,83.6,83.2,72.0,70.3,69.0,67.1.IR(薄膜):νmax(cm-1)＝3082,2987,2919,1698,1585,1561,1490,1416,1297,1264,1223,1154,1103,1088,1045,1000,989,959,880,858,832,814,780,741,702,648,617.HRMS(ESI)计算值C16H13[56Fe]ND3[M+H]+:281.0815.实测值:281.0823.手性柱Daicel Chiralcel OD-H(4.6×250mm),正己烷/异丙醇＝70/30,0.7mL/min,λ＝254nm,t(minor)＝9.82min,t(major)＝11.14min.
eeSM＝98.74％；eePR＝93.08％；Calculated conversion,C＝eeSM/(eeSM+eePR)＝51％；Selectivity(s)＝ln[(1-C)(1-eeSM)]/ln[(1-C)(1+eeSM)]＝141.
实施例4
卤代芳烃III为对甲氧基溴苯，36.5mg,46％yield,93％ee.分析数据:[α]D 29＝-2.6(c＝0.1丙酮).1H NMR(400MHz,CDCl3)δ8.59(d,J＝4.4Hz,1H),7.51(td,J＝7.6,1.6Hz,1H),7.41(d,J＝8.0Hz,1H),7.17-7.10(m,3H),6.71(d,J＝8.4Hz,2H),4.46(d,J＝2.4Hz,1H),4.34(d,J＝2.4Hz,1H),4.10(s,5H),3.78(s,3H),2.63-2.45(m,2H),1.15(t,J＝7.6Hz,3H).13C NMR(101MHz,CDCl3)δ158.2,157.8,148.8,134.8 130.4,130.3,126.9,120.8,113.1,91.7,87.3,85.7,71.4,67.3,66.9,55.1,21.3,14.6.IR(薄膜):νmax(cm-1)＝2964,2932,2903,2834,1609,1585,1562,1518,1481,1454,1432,1374,1299,1272,1242,1175,1149,1104,1078,1032,1000,906,830,813,786,728,677,645,620.HRMS(ESI)计算值C24H24[56Fe]NO[M+H]+:398.1202.实测值:398.1208.手性柱Daicel Chiralpak AD-H(4.6×250mm),正己烷/异丙醇＝90/10,1.0mL/min,λ＝254nm,t(major)＝4.76min,t(minor)＝7.36min.
深红色液体,27.4mg,47％yield,>99％ee.分析数据:[α]D 29＝-172.9(c＝0.1丙酮).1H NMR(400MHz,CDCl3)δ8.54(d,J＝4.8Hz,1H),7.61-7.52(m,2H),7.10-7.06(m,1H),4.69(s,1H),4.30(s,1H),4.24(s,1H),4.03(s,5H),2.91-2.70(m,2H),1.23(t,J＝7.6Hz,3H).13C NMR(101MHz,CDCl3)δ160.1,148.9,135.4,122.3,120.3,90.4,83.1,70.0,69.6,68.9,67.0,22.2,14.9.IR(薄膜):νmax(cm-1)＝3089,2964,2920,1584,1563,1487,1452,1415,1372,1316,1292,1263,1234,1213,1150,1104,1087,1069,1045,998,938,880,812,784,740,708,690,635,610.HRMS(ESI)计算值C17H18[56Fe]N[M+H]+:292.0783.实测值:292.0790.手性柱Daicel Chiralcel OJ-H(4.6×250mm),正己烷/异丙醇＝95/05,1.0mL/min,λ＝254nm,t(major)＝5.82min,t(minor)＝7.50min.
eeSM＝99.86％；eePR＝92.52％；Calculated conversion,C＝eeSM/(eeSM+eePR)＝52％；Selectivity(s)＝ln[(1-C)(1-eeSM)]/ln[(1-C)(1+eeSM)]＝184.
实施例5
卤代芳烃III为对甲氧基溴苯，39.4mg,46％yield,89％ee.分析数据:[α]D 27＝+256.6(c＝0.1丙酮).1H NMR(400MHz,CD2Cl2)δ8.50(ddd,J＝4.8,2.0,0.8Hz,1H),7.51(td,J＝7.6,1.6Hz,1H),7.46(dt,J＝8.0,1.6Hz,1H),7.11(ddd,J＝7.2,4.8,1.6Hz,1H),7.08-7.04(m,2H),6.66-6.62(m,2H),4.78(d,J＝2.4Hz,1H),4.72(d,J＝2.4Hz,1H),4.51(s,5H),3.73(s,3H),2.04(s,3H).13C NMR(101MHz,CD2Cl2)δ158.9,158.1,149.3,135.9,131.7,130.5,128.8,121.8,113.6,93.6,93.2,89.1,73.9,72.6,71.6,55.9,15.2.IR(薄膜):νmax(cm-1)＝2964,2931,2835,1610,1587,1562,1520,1482,1458,1432,1299,1284,1243,1176,1100,1078,1033,997,832,809,788,746.HRMS(ESI)计算值C23H22RuNO[M+H]+:430.0739.实测值:430.0740.手性柱Daicel Chiralpak AD-H(4.6×250mm),正己烷/异丙醇＝80/20,0.7mL/min,λ＝254nm,t(major)＝6.33min,t(minor)＝10.61min.
26.5mg,41％yield,>99％ee.分析数据:[α]D 27＝-126.9(c＝0.1丙酮).1H NMR(400MHz,CD2Cl2)δ8.46-8.44(m,1H),7.57(td,J＝7.6,1.6Hz,1H),7.53-7.50(m,1H),7.10-7.06(m,1H),5.01(dd,J＝2.4,1.2Hz,1H),4.69(m,1H),4.56(t,J＝2.4Hz,1H),4.44(s,5H),2.27(s,3H).13C NMR(101MHz,CD2Cl2)δ159.7,149.3,136.3,123.9,121.4,90.1,87.7,75.0,72.7,72.4,69.8,16.0.IR(薄膜):νmax(cm-1)＝2948,2906,1585,1559,1493,1450,1414,1378,1262,1215,1155,1097,1071,1042,996,806,781,741,706,659,640,617.HRMS(ESI)计算值C16H16RuN[M+H]+:324.0321.实测值:324.0325.手性柱Daicel Chiralcel OD-H(4.6×250mm),正己烷/异丙醇＝95/05,1.0mL/min,λ＝254nm,t(minor)＝8.22min,t(major)＝10.24min.
eeSM＝99.76％；eePR＝88.64％；Calculated conversion,C＝eeSM/(eeSM+eePR)＝53％；Selectivity(s)＝ln[(1-C)(1-eeSM)]/ln[(1-C)(1+eeSM)]＝109.
实施例6
卤代芳烃III为对甲氧基溴苯，36.4mg,42％yield,93％ee.分析数据:[α]D 27＝+105.8(c＝0.1丙酮).1H NMR(400MHz,CD2Cl2)δ8.54-8.51(m,1H),7.53(td,J＝8.0,2.0Hz,1H),7.47(dt,J＝7.6,1.2Hz,1H),7.13(ddd,J＝7.2,4.8,1.2Hz,1H),7.08-7.04(m,2H),6.66-6.62(m,2H),4.79(d,J＝2.4Hz,1H),4.73(d,J＝2.4Hz,1H),4.52(s,5H),3.73(s,3H).13C NMR(101MHz,CD2Cl2)δ158.9,157.9,149.1,136.1,131.7,130.5,129.0,121.9,113.6,73.9,72.6,71.6,55.9.IR(薄膜):νmax(cm-1)＝2963,2930,2834,1609,1586,1562,1519,1481,1454,1431,1298,1284,1242,1175,1099,1079,1032,996,903,831,808,787,746.HRMS(ESI)计算值C23H19RuNOD3[M+H]+:433.0928.实测值:433.0937.手性柱DaicelChiralpak AD-H(4.6×250mm),正己烷/异丙醇＝80/20,0.7mL/min,λ＝254nm,t(major)＝6.34min,t(minor)＝10.60min.
30.6mg,47％yield,89％ee.分析数据:[α]D 27＝-187.7(c＝0.1丙酮).1H NMR(400MHz,CD2Cl2)δ8.47-8.44(m,1H),7.57(td,J＝8.0,2.0Hz,1H),7.51(dt,J＝8.0,1.6Hz,1H),7.08(ddd,J＝7.2,4.8,1.2Hz,1H),5.02(dd,J＝2.4,1.2Hz,1H),4.69(dd,J＝2.4,1.2Hz,1H),4.56(t,J＝2.4Hz,1H),4.44(s,5H).13C NMR(101MHz,CD2Cl2)δ159.7,149.3,136.3,123.9,121.3,90.1,87.5,75.0,72.7,72.4,69.8.IR(薄膜):νmax(cm-1)＝2948,2906,1585,1559,1493,1450,1414,1378,1295,1263,1215,1155,1097,1071,1041,996,889,806,780,741,706,660,640,617.HRMS(ESI)计算值C16H13RuND3[M+H]+:327.0509.实测值:327.0516.手性柱Daicel Chiralcel OD-H(4.6×250mm),正己烷/异丙醇＝95/05,1.0mL/min,λ＝254nm,t(minor)＝8.38min,t(major)＝10.47min.
eeSM＝89.20％；eePR＝93.16％；Calculated conversion,C＝eeSM/(eeSM+eePR)＝49％；Selectivity(s)＝ln[(1-C)(1-eeSM)]/ln[(1-C)(1+eeSM)]＝85.
实施例7
卤代芳烃III为对甲氧基溴苯，39.9mg,45％yield,94％ee.分析数据:[α]D 27＝+10.6(c＝0.1丙酮).1H NMR(400MHz,CD2Cl2)δ8.49(ddd,J＝4.8,2.0,1.2Hz,1H),7.52(td,J＝7.6,1.6Hz,1H),7.49-7.46(m,1H),7.11(ddd,J＝7.2,4.8,1.6Hz,1H),7.08-7.03(m,2H),6.64-6.61(m,2H),4.81(d,J＝2.4Hz,1H),4.70(d,J＝2.4Hz,1H),4.55(s,5H),3.73(s,3H),2.42-2.32(m,1H),2.25-2.15(m,1H),1.04(t,J＝7.6Hz,3H).13C NMR(101MHz,CD2Cl2)δ158.9,158.0,149.3,135.9,131.6,130.5,129.0,121.8,113.6,96.7,93.4,93.2,73.7,71.3,70.4,55.9,21.8,16.0.IR(薄膜):νmax(cm-1)＝2962,2930,2834,1609,1586,1562,1519,1481,1454,1431,1298,1284,1269,1242,1175,1099,1080,1032,996,831,808,787,744,701.HRMS(ESI)计算值C24H24RuNO[M+H]+:444.0896.实测值:444.0896.手性柱Daicel Chiralcel OD-H(4.6×250mm),正己烷/异丙醇＝90/10,1.0mL/min,λ＝254nm,t(major)＝5.96min,t(minor)＝6.80min.
29.6mg,44％yield,80％ee.分析数据:[α]D 27＝-264.8(c＝0.1丙酮).1H NMR(400MHz,CD2Cl2)δ8.46-8.43(m,1H),7.56(td,J＝7.6,1.6Hz,1H),7.49(dd,J＝8.0,1.2Hz,1H),7.07(ddd,J＝7.6,4.8,1.6Hz,1H),5.00(dd,J＝2.4,1.6Hz,1H),4.69-4.67(m,1H),4.58(t,J＝2.4Hz,1H),4.47(s,5H),2.70-2.60(m,1H),2.59-2.48(m,1H),1.14(t,J＝7.6Hz,3H).13C NMR(101MHz,CD2Cl2)δ159.7,149.3,136.2,124.3,121.4,95.3,89.9,72.53,72.51,69.8,22.3,16.2.IR(薄膜):νmax(cm-1)＝2970,2948,2906,1585,1559,1493,1450,1414,1378,1262,1155,1097,1071,1042,996,807,781,741,660,641.HRMS(ESI)计算值C17H18RuN[M+H]+:338.0477.实测值:338.0481.手性柱Daicel Phenomenex Lux 5uCellulose-2(4.6×250mm),正己烷/异丙醇＝98/02,0.7mL/min,λ＝254nm,t(major)＝11.23min,t(minor)＝12.15min.
eeSM＝79.60％；eePR＝94.40％；Calculated conversion,C＝eeSM/(eeSM+eePR)＝46％；Selectivity(s)＝ln[(1-C)(1-eeSM)]/ln[(1-C)(1+eeSM)]＝85.
实施例8
卤代芳烃III为对甲氧基溴苯，38.3mg,45％yield,96％ee.分析数据:[α]D 29＝+18.3(c＝0.1丙酮).1H NMR(400MHz,CD2Cl2)δ8.55(ddd,J＝5.2,2.0,1.2Hz,1H),7.56(td,J＝7.6,2.0Hz,1H),7.45(dt,J＝8.0,1.2Hz,1H),7.17-7.11(m,3H),6.71-6.68(m,2H),4.48(d,J＝2.4Hz,1H),4.34(d,J＝2.4Hz,1H),4.09(s,5H),3.76(s,3H),2.60-2.52(m,1H),2.45-2.36(m,1H),1.49-1.40(m,2H),1.33-1.23(m,2H),0.85(t,J＝7.6Hz,3H).13C NMR(101MHz,CD2Cl2)δ158.9,158.8,149.6,135.7,131.4,131.0,127.6,121.6,113.8,91.3,87.7,87.1,72.2,68.5,67.9,55.9,33.9,28.7,23.6,14.5.IR(薄膜):νmax(cm-1)＝2954,2927,2856,1737,1609,1584,1562,1519,1480,1457,1432,1374,1299,1274,1242,1175,1150,1104,1033,1000,914,830,812,787,746,704,620.HRMS(ESI)计算值C26H28[56Fe]NO[M+H]+:426.1515.实测值:426.1515.手性柱Daicel Chiralcel OD-H(4.6×250mm),正己烷/异丙醇＝90/10,1.0mL/min,λ＝254nm,t(minor)＝4.52min,t(major)＝4.99min.
26.8mg,42％yield,>99％ee.分析数据:[α]D 29＝-19.1(c＝0.1丙酮).1H NMR(400MHz,CD2Cl2)δ8.52(ddd,J＝4.8,1.6,0.8Hz,1H),7.64-7.59(m,1H),7.55(dt,J＝8.0,1.2Hz,1H),7.10(ddd,J＝7.2,4.8,1.2Hz,1H),4.69-4.67(m,1H),4.31(t,J＝2.4Hz,1H),4.25(t,J＝2.4Hz,1H),4.03(s,5H),3.03-2.95(m,1H),2.67-2.58(m,1H),1.64-1.49(m,2H),1.45-1.35(m,2H),0.95(t,J＝7.2Hz,3H).13C NMR(101MHz,CD2Cl2)δ161.0,149.6,136.2,123.0,121.0,90.0,83.9,71.4,70.9,69.5,67.9,34.1,29.7,23.7,14.7.IR(薄膜):νmax(cm-1)＝3089,2954,2925,2856,1584,1562,1487,1455,1416,1377,1288,1263,1237,1215,1149,1104,1089,1068,1044,998,960,879,813,784,739,697,675,651,609.HRMS(ESI)计算值C19H22[56Fe]N[M+H]+:320.1096.实测值:320.1091.手性柱Daicel ChiralpakIG(4.6×250mm),正己烷/异丙醇＝90/10,0.9mL/min,λ＝254nm,t(major)＝4.47min,t(minor)＝4.84min.
eeSM＝99.94％；eePR＝95.68％；Calculated conversion,C＝eeSM/(eeSM+eePR)＝51％；Selectivity(s)＝ln[(1-C)(1-eeSM)]/ln[(1-C)(1+eeSM)]＝365.
实施例9
卤代芳烃III为对甲氧基溴苯，34.7mg,41％yield,96％ee.分析数据:[α]D 29＝+20.9(c＝0.1丙酮).1H NMR(400MHz,CD2Cl2)δ8.57-8.54(m,1H),7.55(td,J＝7.6,2.0Hz,1H),7.44(dt,J＝8.0,1.2Hz,1H),7.17-7.13(m,3H),6.73-6.69(m,2H),4.51(d,J＝2.8Hz,2H),4.09(s,5H),3.77(s,3H),2.41(d,J＝6.8Hz,2H),0.96-0.86(m,1H),0.47-0.37(m,2H),0.15-0.09(m,1H),0.04--0.07(m,1H).13C NMR(101MHz,CD2Cl2)δ158.9,158.8,149.6,135.7,131.3,131.1,127.7,121.7,113.8,90.7,87.9,86.9,72.3,68.7,68.1,55.9,33.9,12.4,5.5,4.9.IR(薄膜):νmax(cm-1)＝3074,2996,2904,2834,1711,1609,1584,1562,1519,1481,1456,1431,1358,1286,1242,1220,1175,1148,1104,1073,1031,1000,963,930,910,814,787,746,702,685,650.HRMS(ESI)计算值C26H26[56Fe]NO[M+H]+:424.1358.实测值:424.1361.手性柱Daicel Chiralpak AD-H(4.6×250mm),正己烷/异丙醇＝95/05,0.8mL/min,λ＝254nm,t(major)＝7.28min,t(minor)＝11.20min.
25.4mg,40％yield,>99％ee.分析数据:[α]D 29＝-97.6(c＝0.1丙酮).1H NMR(400MHz,CD2Cl2)δ8.49(d,J＝4.8Hz,1H),7.64-7.59(m,1H),7.56(d,J＝7.6Hz,1H),7.10(dd,J＝8.0,4.8Hz,1H),4.73(s,1H),4.51(s,1H),4.31(s,1H),4.06(s,5H),2.84(dd,J＝15.2,6.8Hz,1H),2.59(dd,J＝15.2,6.8Hz,1H),1.08-1.01(m,1H),0.53-0.43(m,2H),0.23-0.13(m,2H).13C NMR(101MHz,CD2Cl2)δ160.9,149.4,136.4,123.0,121.1,89.5,83.8,71.7,71.2,69.8,68.3,34.7,12.4,5.5,5.0.IR(薄膜):νmax(cm-1)＝3074,2996,2902,1584,1562,1487,1455,1417,1290,1254,1150,1104,1086,1067,1042,1013,998,957,928,882,814,784,738,698,673,649,619,606.HRMS(ESI)计算值C19H20[56Fe]N[M+H]+:318.0940.实测值:318.0932.手性柱Daicel Chiralcel OD-H(4.6×250mm),正己烷/异丙醇＝90/10,0.9mL/min,λ＝254nm,t(major)＝5.57min,t(minor)＝9.28min.
eeSM＝99.88％；eePR＝96.08％；Calculated conversion,C＝eeSM/(eeSM+eePR)＝51％；Selectivity(s)＝ln[(1-C)(1-eeSM)]/ln[(1-C)(1+eeSM)]＝369.
实施例10
卤代芳烃III为对甲氧基溴苯，41.0mg,45％yield,97％ee.分析数据:[α]D 23＝+40.1(c＝0.1丙酮).1H NMR(400MHz,CD2Cl2)δ8.61(ddd,J＝4.8,2.0,0.8Hz,1H),7.52(td,J＝7.6,1.6Hz,1H),7.33(dt,J＝8.0,1.2Hz,1H),7.21-7.11(m,6H),7.06(dd,J＝6.8,1.6Hz,2H),6.73-6.70(m,2H),4.53(d,J＝2.4Hz,1H),4.32(d,J＝2.4Hz,1H),4.14(s,5H),4.08(AB,JAB＝15.2Hz,1H),3.772(s,3H),3.770(BA,JBA＝15.2Hz,1H).13C NMR(101MHz,CD2Cl2)δ158.9,158.6,149.7,142.8,135.7,131.2,131.1,129.3,128.8,127.6,126.5,121.8,113.8,90.2,87.8,87.0,72.5,69.3,68.3,55.9,35.0.IR(薄膜):νmax(cm-1)＝3025,2997,2906,2833,1607,1584,1562,1518,1480,1451,1431,1284,1266,1242,1175,1148,1105,1074,1030,999,953,915,815,787,772,732,700,654.HRMS(ESI)计算值C29H26[56Fe]NO[M+H]+:460.1358.实测值:460.1356.手性柱Daicel Chiralpak AD-H(4.6×250mm),正己烷/异丙醇＝80/20,0.7mL/min,λ＝286nm,t(major)＝6.52min,t(minor)＝7.29min.
31.6mg,45％yield,93％ee.分析数据:[α]D 25＝-153.4(c＝0.1丙酮).1H NMR(400MHz,CD2Cl2)δ8.53(ddd,J＝4.8,2.0,1.2Hz,1H),7.59(td,J＝8.0,2.0Hz,1H),7.51-7.48(m,1H),7.23-7.21(m,4H),7.16-7.08(m,2H),4.72(dd,J＝2.8,1.6Hz,1H),4.63(AB,JAB＝15.2Hz,1H),4.29(t,J＝2.4Hz,1H),4.25(dd,J＝2.4,1.6Hz,1H),4.07(s,5H),3.96(BA,JBA＝15.2Hz,1H).13C NMR(101MHz,CD2Cl2)δ160.7,149.6,143.3,136.4,129.4,128.8,126.4,122.7,121.2,88.7,83.7,72.4,71.1,69.5,68.5,35.8.IR(薄膜):νmax(cm-1)＝3082,3058,3024,2999,2917,2849,1658,1631,1583,1562,1488,1451,1416,1296,1150,1104,1087,1068,1031,996,970,814,784,739,716,697,651,611.HRMS(ESI)计算值C22H20[56Fe]N[M+H]+:354.0940.实测值:354.0940.手性柱Daicel Chiralcel OD-H(4.6×250mm),正己烷/异丙醇＝95/05,0.7mL/min,λ＝286nm,t(major)＝10.35min,t(minor)＝11.11min.
eeSM＝93.30％；eePR＝96.50％；Calculated conversion,C＝eeSM/(eeSM+eePR)＝49％；Selectivity(s)＝ln[(1-C)(1-eeSM)]/ln[(1-C)(1+eeSM)]＝195.
实施例11
卤代芳烃III为对甲氧基溴苯，35.2mg,42％yield,99％ee.分析数据:[α]D 26＝+32.6(c＝0.1丙酮).1H NMR(400MHz,CD2Cl2)δ8.6(dd,J＝4.8,1.2Hz,1H),7.53(td,J＝7.6,2.0Hz,1H),7.34(dt,J＝8.0,1.2Hz,1H),7.17-7.12(m,3H),6.71(d,J＝8.8Hz,2H),4.56-4.53(m,2H),4.42(d,J＝2.4Hz,1H),4.36(d,J＝2.4Hz,1H),4.11(s,5H),3.77(s,3H),3.46(AB,JAB＝15.6Hz,1H),3.14(BA,JBA＝15.6Hz,1H),1.56(s,3H).13C NMR(101MHz,CD2Cl2)δ158.8,158.7,149.7,146.6,135.7,131.3,131.1,127.4,121.7,113.8,111.0,88.5,87.6,87.4,72.4,69.6,67.9,55.9,37.2,23.0.IR(薄膜):νmax(cm-1)＝2963,2921,2851,1609,1584,1562,1519,1480,1431,1373,1282,1242,1175,1149,1104,1075,1032,999,886,813,787,743,703.HRMS(ESI)计算值C26H26[56Fe]NO[M+H]+:424.1358.实测值:424.1362.手性柱Daicel Chiralcel OD-H(4.6×250mm),正己烷/异丙醇＝90/10,0.7mL/min,λ＝286nm,t(major)＝6.12min,t(minor)＝6.75min.
31.1mg,49％yield,90％ee.分析数据:[α]D 26＝-71.5(c＝0.1丙酮).1H NMR(400MHz,CD2Cl2)δ8.52(dd,J＝4.8,1.2Hz,1H),7.58(td,J＝7.6,1.6Hz,1H),7.47(dt,J＝8.0,1.2Hz,1H),7.09(ddd,J＝7.6,4.8,1.2Hz,1H),4.74-4.72(m,1H),4.66-4.64(m,1H),4.53-4.52(m,1H),4.31-4.28(m,2H),4.03(s,5H),3.94(AB,JAB＝15.6Hz,1H),3.28(BA,JBA＝15.6Hz,1H),1.71(s,3H).13C NMR(101MHz,CD2Cl2)δ160.6,149.7,147.2,136.3,122.6,121.2,110.9,86.7,84.4,72.6,71.0,69.4,68.3,38.0,23.3.IR(薄膜):νmax(cm-1)＝3086,2933,2881,1649,1584,1562,1485,1436,1415,1365,1326,1280,1221,1181,1157,1102,1080,1040,994,970,884,831,808,784,742,698,648,623,607.HRMS(ESI)计算值C19H20[56Fe]N[M+H]+:318.0940.实测值:318.0931.手性柱Daicel Chiralcel OD-H(4.6×250mm),正己烷/异丙醇＝90/10,0.7mL/min,λ＝286nm,t(major)＝6.17min,t(minor)＝6.91min.
eeSM＝89.60％；eePR＝98.92％；Calculated conversion,C＝eeSM/(eeSM+eePR)＝48％；Selectivity(s)＝ln[(1-C)(1-eeSM)]/ln[(1-C)(1+eeSM)]＝565.
实施例12
卤代芳烃III为对甲氧基溴苯，35.8mg,41％yield,95％ee.分析数据:[α]D 29＝-64.5(c＝0.1丙酮).1H NMR(400MHz,CD2Cl2)δ8.57(ddd,J＝4.8,2.0,0.8Hz,1H),7.55(td,J＝7.6,2.0Hz,1H),7.43(dt,J＝8.0,1.2Hz,1H),7.17-7.12(m,3H),6.72-6.69(m,2H),5.29(tt,J＝7.2,1.2Hz,1H),4.48(d,J＝2.4Hz,1H),4.32(d,J＝2.4Hz,1H),4.11(s,5H),3.76(s,3H),3.25-3.10(m,2H),1.70(s,3H),1.58(s,3H).13C NMR(101MHz,CD2Cl2)δ158.82,158.78,149.6,135.7,132.1,131.3,131.1,127.6,124.4,121.7,113.8,90.5,88.0,86.7,72.3,68.5,68.2,55.9,27.5,26.2,18.3.IR(薄膜):νmax(cm-1)＝2966,2910,2834,1609,1584,1562,1519,1481,1451,1432,1375,1284,1268,1242,1175,1148,1104,1074,1032,999,914,890,830,813,787,744,700,652.HRMS(ESI)计算值C27H28[56Fe]NO[M+H]+:438.1515.实测值:438.1512.手性柱Daicel Chiralpak AD-H(4.6×250mm),正己烷/异丙醇＝95/05,0.8mL/min,λ＝254nm,t(major)＝6.23min,t(minor)＝9.70min.
25.2mg,38％yield,>99％ee.分析数据:[α]D 29＝+19.4(c＝0.1丙酮).1H NMR(400MHz,CD2Cl2)δ8.52(ddd,J＝4.8,1.6,0.8Hz,1H),7.61(td,J＝7.6,2.0Hz,1H),7.53(dt,J＝8.0,1.2Hz,1H),7.10(ddd,J＝7.2,4.8,1.2Hz,1H),5.42-5.37(m,1H),4.69(dd,J＝2.8,1.6Hz,1H),4.27(t,J＝2.0Hz,1H),4.25(t,J＝2.4Hz,1H),4.04(s,5H),3.57(dd,J＝16.0,7.6Hz,1H),3.44(dd,J＝16.0,7.6Hz,1H),1.75(s,3H),1.72(s,3H).13C NMR(101MHz,CD2Cl2)δ160.8,149.6,136.3,132.1,124.9,123.1,121.1,89.1,83.8,71.3,70.9,69.7,68.1,28.4,26.2,18.5.IR(薄膜):νmax(cm-1)＝3089,2966,2913,2855,1584,1562,1487,1446,1416,1372,1288,1256,1164,1149,1129,1103,1044,997,914,881,812,785,741,698,671,609.HRMS(ESI)计算值C20H22[56Fe]N[M+H]+:332.1096.实测值:332.1092.手性柱Daicel Chiralcel OD-H(4.6×250mm),正己烷/异丙醇＝95/05,1.0mL/min,λ＝254nm,t(major)＝5.26min,t(minor)＝7.29min.eeSM＝99.82％；eePR＝94.70％；Calculated conversion,C＝eeSM/(eeSM+eePR)＝51％；Selectivity(s)＝ln[(1-C)(1-eeSM)]/ln[(1-C)(1+eeSM)]＝255.
实施例13
卤代芳烃III为对甲氧基溴苯，38.2mg,45％yield,95％ee.分析数据:[α]D 26＝-569.5(c＝0.1丙酮).1H NMR(400MHz,CD2Cl2)δ8.56(ddd,J＝4.8,1.6,0.8Hz,1H),7.58(td,J＝8.0,2.0Hz,1H),7.49(dt,J＝8.0,1.2Hz,1H),7.18-7.12(m,3H),6.71(d,J＝8.8Hz,2H),6.07(s,1H),4.64(d,J＝2.4Hz,1H),4.61(d,J＝2.4Hz,1H),4.09(s,5H),3.77(s,3H),1.82(s,3H),1.78(s,3H).13C NMR(101MHz,CD2Cl2)δ158.9,158.7,149.5,135.7,134.5,131.14,131.09,128.0,121.7,121.1,113.8,88.2,87.0,85.3,72.6,69.1,68.8,55.9,27.5,20.3.IR(薄膜):νmax(cm-1)＝2957,2918,2849,1609,1583,1562,1518,1480,1449,1431,1395,1374,1282,1243,1203,1175,1156,1104,1077,1031,998,813,787,733,700.HRMS(ESI)计算值C26H26[56Fe]NO[M+H]+:424.1358.实测值:424.1367.手性柱DaicelChiralcel OD-H(4.6×250mm),正己烷/异丙醇＝90/10,0.7mL/min,λ＝286nm,t(major)＝8.89min,t(minor)＝9.57min.
28.7mg,45％yield,99％ee.分析数据:[α]D 27＝+237.1(c＝0.1丙酮).1H NMR(400MHz,CD2Cl2)δ8.52(d,J＝4.4Hz,1H),7.64-7.57(m,2H),7.10(ddd,J＝6.8,4.8,2.4Hz,1H),6.43(s,1H),4.83-4.81(m,1H),4.50-4.48(m,1H),4.37-4.36(m,1H),4.03(s,5H),1.87(s,3H),1.76(s,3H).13C NMR(101MHz,CD2Cl2)δ160.4,149.7,136.2,135.1,123.6,122.0,121.2,84.7,84.1,71.7,71.3,69.8,68.7,27.1,20.2.IR(薄膜):νmax(cm-1)＝2969,2918,2850,1584,1559,1487,1449,1415,1376,1224,1154,1102,1088,1077,1048,998,834,813,785,743,692.HRMS(ESI)计算值C19H20[56Fe]N[M+H]+:318.0940.实测值:318.0947.手性柱Daicel Chiralcel OD-H(4.6×250mm),正己烷/异丙醇＝90/10,0.7mL/min,λ＝286nm,t(major)＝6.35min,t(minor)＝7.60min.eeSM＝99.18％；eePR＝94.90％；Calculated conversion,C＝eeSM/(eeSM+eePR)＝51％；Selectivity(s)＝ln[(1-C)(1-eeSM)]/ln[(1-C)(1+eeSM)]＝209.
实施例14
卤代芳烃III为对甲氧基溴苯，39.7mg,45％yield,98％ee.分析数据:[α]D 29＝+127.6(c＝0.1丙酮).1H NMR(400MHz,CDCl3)δ8.53-8.51(m,1H),7.46(td,J＝8.0,2.0Hz,1H),7.40(d,J＝7.6Hz,1H),7.24-7.19(m,2H),7.11(ddd,J＝7.2,4.8,1.2Hz,1H),6.76-6.72(m,2H),4.65(d,J＝2.4Hz,1H),4.34(d,J＝2.4Hz,1H),4.13(s,5H),3.78(s,3H),0.19(s,9H).13C NMR(101MHz,CDCl3)δ158.8,158.0,148.1,134.6,130.6,130.0,126.4,121.0,113.2,91.4,91.2,74.1,73.2,73.0,71.0,55.2,0.6.IR(薄膜):νmax(cm-1)＝2969,2902,1608,1585,1520,1476,1461,1430,1408,1384,1293,1261,1243,1197,1178,1141,1106,1070,1051,1019,1001,951,906,814,786,748,688,659,632,615.HRMS(ESI)计算值C25H28[56Fe]NOSi[M+H]+:442.1284.实测值:442.1286.手性柱Daicel Chiralpak IC-3(4.6×250mm),正己烷/异丙醇＝95/05,0.7mL/min,λ＝254nm,t(major)＝6.60min,t(minor)＝7.13min.
29.5mg,44％yield,>99％ee.分析数据:[α]D 29＝-223.8(c＝0.1丙酮).1H NMR(400MHz,CDCl3)δ8.43(d,J＝4.8Hz,1H),7.56(td,J＝8.0,1.6Hz,1H),7.51(d,J＝8.0Hz,1H),7.06(ddd,J＝7.2,5.2,1.6Hz,1H),4.86(s,1H),4.50(t,J＝2.4Hz,1H),4.34(s,1H),4.08(s,5H),0.32(s,9H).13C NMR(101MHz,CDCl3)δ159.6,148.1,135.4,121.2,120.4,89.9,76.5,72.0,71.7,71.3,69.6,1.2.IR(薄膜):νmax(cm-1)＝2974,2953,2900,1585,1561,1485,1443,1411,1331,1237,1148,1130,1105,1062,1041,998,942,830,809,786,745,683,662,633,619.HRMS(ESI)计算值C18H22[56Fe]NSi[M+H]+:336.0865.实测值:336.0865.手性柱Daicel Chiralcel OJ-3(SFC:3.0mm,I.D.:150mm),CO2/MeOH＝98/02,1.0mL/min,λ＝214nm,t(minor)＝3.00min,t(major)＝3.32min.eeSM＝99.26％；eePR＝97.82％；Calculated conversion,C＝eeSM/(eeSM+eePR)＝50％；Selectivity(s)＝ln[(1-C)(1-eeSM)]/ln[(1-C)(1+eeSM)]＝508.
实施例15
卤代芳烃III为对甲氧基溴苯，38.9mg,40％yield,97％ee.分析数据:[α]D 27＝+157.2(c＝0.1丙酮).1H NMR(400MHz,CD2Cl2)δ8.48(ddd,J＝4.8,1.6,0.8Hz,1H),7.40(td,J＝7.6,2.0Hz,1H),7.27(dt,J＝8.0,1.2Hz,1H),7.11-7.06(m,3H),6.68-6.64(m,2H),4.97(d,J＝2.4Hz,1H),4.61(d,J＝2.4Hz,1H),4.55(s,5H),3.74(s,3H),0.04(s,9H).13CNMR(101MHz,CD2Cl2)δ159.1,158.8,148.8,135.5,132.0,129.9,128.3,121.8,113.7,98.1,97.1,78.9,76.4,76.0,73.8,55.9,1.0.IR(薄膜):νmax(cm-1)＝2963,1610,1586,1520,1482,1432,1243,1175,1100,1033,997,831,809,787,746.HRMS(ESI)计算值C25H28RuNOSi[M+H]+:488.0978.实测值:488.0982.手性柱Daicel Chiralcel OD-H(4.6×250mm),正己烷/异丙醇＝95/05,0.7mL/min,λ＝254nm,t(major)＝6.17min,t(minor)＝7.18min.
37.3mg,49％yield,68％ee.分析数据:[α]D 27＝-73.4(c＝0.1丙酮).1H NMR(400MHz,CD2Cl2)δ8.38(ddd,J＝4.8,2.0,1.2Hz,1H),7.52(td,J＝7.6,2.0Hz,1H),7.41(dd,J＝8.0,1.2Hz,1H),7.05(ddd,J＝7.6,4.8,1.2Hz,1H),5.17(dd,J＝2.4,1.2Hz,1H),4.81(t,J＝2.4Hz,1H),4.61(dd,J＝2.4,1.2Hz,1H),4.48(s,5H),0.19(s,9H).13C NMR(101MHz,CD2Cl2)δ159.6,148.6,136.2,122.9,121.4,95.6,78.6,76.9,75.1,73.5,72.5,1.5.IR(薄膜):νmax(cm-1)＝2987,2947,2906,1585,1559,1493,1450,1414,1378,1262,1155,1097,1071,1042,996,807,781,741,641.HRMS(ESI)计算值C18H22NRuSi[M+H]+:382.0560.实测值:382.0553.手性柱Daicel Chiralcel OD-H(4.6×250mm),正己烷/异丙醇＝95/05,0.7mL/min,λ＝254nm,t(minor)＝5.68min,t(major)＝6.18min.eeSM＝68.28％；eePR＝97.10％；Calculated conversion,C＝eeSM/(eeSM+eePR)＝41％；Selectivity(s)＝ln[(1-C)(1-eeSM)]/ln[(1-C)(1+eeSM)]＝140.
实施例16
卤代芳烃III为对甲氧基溴苯，40.6mg,42％yield,93％ee.分析数据:[α]D 27＝+131.9(c＝0.1丙酮).1H NMR(400MHz,CD2Cl2)δ8.52(d,J＝5.2Hz,1H),7.50-7.46(m,1H),7.39(d,J＝7.6Hz,1H),7.18-7.11(m,3H),6.74-6.71(m,2H),4.69(d,J＝2.4Hz,1H),4.34(d,J＝2.4Hz,1H),4.15(s,5H),3.77(s,3H),0.96(t,J＝8.0Hz,9H),0.80-0.63(m,6H).13CNMR(101MHz,CD2Cl2)δ159.7,158.9,149.0,135.3,131.3,130.9,127.5,121.8,113.9,92.4,91.8,75.2,73.3,72.4,71.9,55.9,8.6,5.8.IR(薄膜):νmax(cm-1)＝2949,2905,2871,2833,1609,1586,1561,1519,1478,1459,1429,1386,1295,1260,1241,1197,1175,1138,1105,1075,1033,1003,966,950,815,787,722,693.HRMS(ESI)计算值C28H34[56Fe]NOSi[M+H]+:484.1754.实测值:484.1748.手性柱Daicel Phenomenex Lux 5u Cellulose-2(4.6×250mm),正己烷/异丙醇＝98/02,0.7mL/min,λ＝286nm,t(major)＝6.09min,t(minor)＝6.64min.
36.8mg,49％yield,80％ee.分析数据:[α]D 27＝-85.5(c＝0.1丙酮).1H NMR(400MHz,CD2Cl2)δ8.44(d,J＝4.4Hz,1H),7.59(td,J＝8.0,2.0Hz,1H),7.53(dt,J＝8.0,1.2Hz,1H),7.07(ddd,J＝7.2,4.8,1.2Hz,1H),4.88(dd,J＝2.4,1.2Hz,1H),4.54(t,J＝2.4Hz,1H),4.34(dd,J＝2.4,1.2Hz,1H),4.07(s,5H),1.05-0.98(m,9H),0.98-0.81(m,6H).13C NMR(101MHz,CD2Cl2)δ160.7,148.7,136.3,122.1,121.1,90.3,77.8,72.6,72.2,70.5,70.4,8.9,6.2.IR(薄膜):νmax(cm-1)＝3082,2951,2898,1585,1563,1489,1449,1416,1377,1245,1216,1161,1087,1067,1034,1003,899,824,784,742,690,647,628.HRMS(ESI)计算值C21H28[56Fe]NSi[M+H]+:378.1335.实测值:378.1330.手性柱Daicel Chiralcel OJ-3(SFC:3.0mm,I.D.:150mm),CO2/MeOH＝98/02,1.0mL/min,λ＝286nm,t(minor)＝3.89min,t(major)＝4.46min.eeSM＝79.88％；eePR＝93.20％；Calculated conversion,C＝eeSM/(eeSM+eePR)＝46％；Selectivity(s)＝ln[(1-C)(1-eeSM)]/ln[(1-C)(1+eeSM)]＝70.
实施例17
卤代芳烃III为对甲氧基溴苯，38.4mg,42％yield,90％ee.分析数据:[α]D 26＝+73.9(c＝0.1丙酮).1H NMR(400MHz,CD2Cl2)δ8.39(ddd,J＝4.8,1.2,0.8Hz,1H),8.00(dt,J＝8.0,1.2Hz,1H),7.74(td,J＝7.6,2.0Hz,1H),7.18-7.11(m,3H),6.70(d,J＝8.8Hz,2H),4.79(d,J＝2.4Hz,1H),4.62(d,J＝2.4Hz,1H),4.13(s,5H),3.77(s,3H),0.90(s,9H).13CNMR(101MHz,CD2Cl2)δ158.9,157.5,149.0,135.5,130.84,130.75,129.0,122.0,113.8,92.0,88.3,80.0,77.4,73.1,69.2,55.9,46.5,31.1.IR(薄膜):νmax(cm-1)＝2958,2919,2835,1608,1585,1564,1519,1491,1458,1440,1419,1302,1276,1244,1176,1151,1105,1073,1050,1030,999,984,908,823,787,743,732,694.HRMS(ESI)计算值C26H28[56Fe]NOS[M+H]+:458.1236.实测值:458.1232.手性柱Daicel Chiralcel OD-H(4.6×250mm),正己烷/异丙醇＝98/02,0.7mL/min,λ＝286nm,t(major)＝9.47min,t(minor)＝10.46min.
30.9mg,44％yield,92％ee.分析数据:[α]D 26＝-72.7(c＝0.1丙酮).1H NMR(400MHz,CD2Cl2)δ8.55(dd,J＝8.0,1.2Hz,1H),8.45(dd,J＝4.8,2.0Hz,1H),7.65(td,J＝8.0,2.0Hz,1H),7.12(dd,J＝7.6,5.2Hz,1H),5.07(t,J＝2.4Hz,1H),4.54(t,J＝2.0Hz,1H),4.47(t,J＝2.8Hz,1H),4.08(s,5H),1.05(s,9H).13C NMR(101MHz,CD2Cl2)δ159.2,149.3,135.6,125.0,121.7,88.6,80.2,77.6,71.8,70.8,70.3,46.9,31.1.IR(薄膜):νmax(cm-1)＝2956,2933,2916,2891,2857,1584,1559,1478,1453,1415,1388,1361,1275,1256,1216,1162,1143,1103,1041,1025,1003,989,941,816,788,746,701,662,624,612.HRMS(ESI)计算值C19H22[56Fe]NS[M+H]+:352.0817.实测值:352.0807.手性柱Daicel ChiralcelOD-H(4.6×250mm),正己烷/异丙醇＝95/05,0.7mL/min,λ＝286nm,t(minor)＝6.32min,t(major)＝6.71min.eeSM＝91.60％；eePR＝90.42％；Calculated conversion,C＝eeSM/(eeSM+eePR)＝50％；Selectivity(s)＝ln[(1-C)(1-eeSM)]/ln[(1-C)(1+eeSM)]＝64.
实施例18
卤代芳烃III为对甲氧基溴苯，34.8mg,45％yield,92％ee.分析数据:[α]D 29＝+25.5(c＝0.1丙酮).1H NMR(400MHz,CD2Cl2)δ8.56-8.54(m,1H),7.65(td,J＝7.6,1.2Hz,1H),7.60(dd,J＝8.0,1.2Hz,1H),7.23-7.18(m,3H),6.75(d,J＝8.8Hz,2H),4.63(t,J＝2.8Hz,1H),4.27-4.25(m,1H),4.23(s,5H),3.79(s,3H).13C NMR(101MHz,CD2Cl2)δ159.2,156.1(J＝4.1Hz),149.8,136.2,135.2(J＝274.5Hz),131.3,130.0,126.8(J＝1.9Hz),122.3,113.9,82.2,74.5(J＝9.0Hz),73.11,61.7(J＝3.7Hz),61.66,56.4(J＝15.0Hz),56.0.19F NMR(377MHz,CD2Cl2)δ-188.6(m).IR(薄膜):νmax(cm-1)＝2959,2919,2849,1608,1585,1564,1519,1490,1458,1439,1419,1346,1301,1275,1243,1175,1150,1105,1073,1050,1029,999,983,907,821,786,731,694.HRMS(ESI)计算值C22H19[56Fe]FNO[M+H]+:388.0795.实测值:388.0799.手性柱Daicel Chiralcel OD-H(4.6×250mm),正己烷/异丙醇＝95/05,0.7mL/min,λ＝286nm,t(major)＝15.18min,t(minor)＝18.76min.
25.2mg,45％yield,94％ee.分析数据:[α]D 27＝-68.5(c＝0.1丙酮).1H NMR(400MHz,CD2Cl2)δ8.52(d,J＝3.6Hz,1H),7.73(d,J＝8.0Hz,1H),7.68-7.60(m,1H),7.16-7.12(m,1H),4.70(s,1H),4.58-4.56(m,1H),4.15(s,5H),4.04(t,J＝2.8Hz,1H).13C NMR(101MHz,CD2Cl2)δ157.7(J＝4.7Hz),150.1,136.8,135.3(J＝273.6Hz),122.2(J＝7.5Hz),121.8,72.2(J＝8.3Hz),71.7,62.7,61.9(J＝4.5Hz),58.8(J＝16.1Hz).19F NMR(377MHz,CD2Cl2)δ-186.6.IR(薄膜):νmax(cm-1)＝1584,1563,1501,1462,1444,1422,1382,1363,1298,1284,1240,1217,1151,1136,1102,1046,1019,997,973,810,782,741,711,654,633,617.HRMS(ESI)计算值C15H13[56Fe]NF[M+H]+:282.0376.实测值:282.0377.手性柱DaicelChiralcel OD-H(4.6×250mm),正己烷/异丙醇＝98/02,0.7mL/min,λ＝286nm,t(minor)＝12.06min,t(major)＝12.76min.eeSM＝93.94％；eePR＝92.00％；Calculated conversion,C＝eeSM/(eeSM+eePR)＝51％；Selectivity(s)＝ln[(1-C)(1-eeSM)]/ln[(1-C)(1+eeSM)]＝85.
实施例19
卤代芳烃III为对甲硫基溴苯，38.3mg,48％yield,92％ee.分析数据:[α]D 29＝+89.6(c＝0.1丙酮).1H NMR(400MHz,CDCl3)δ8.59(ddd,J＝4.8,1.6,0.8Hz,1H),7.52(td,J＝8.0,2.0Hz,1H),7.42(d,J＝8.0Hz,1H),7.16-7.11(m,3H),7.07-7.03(m,2H),4.45(d,J＝2.4Hz,1H),4.36(d,J＝2.4Hz,1H),4.07(s,5H),2.46(s,3H),2.14(s,3H).13C NMR(101MHz,CDCl3)δ158.0,148.8,135.6,135.4,134.9,129.8,126.9,125.9,120.9,87.0,85.9,85.1,71.7,69.6,68.0,15.8,14.4.IR(薄膜):νmax(cm-1)＝2985,2917,1584,1561,1502,1480,1452,1428,1409,1392,1376,1310,1263,1184,1147,1103,1070,1053,1011,1001,963,911,892,814,788,733,701,670,635,611.HRMS(ESI)计算值C23H22[56Fe]NS[M+H]+:400.0817.实测值:400.0826.手性柱Daicel Chiralcel OD-H(4.6×250mm),正己烷/异丙醇＝90/10,1.0mL/min,λ＝254nm,t(minor)＝6.54min,t(major)＝7.26min.
II-1.23.7mg,43％yield,>99％ee.eeSM＝99.82％；eePR＝92.24％；Calculatedconversion,C＝eeSM/(eeSM+eePR)＝52％；Selectivity(s)＝ln[(1-C)(1-eeSM)]/ln[(1-C)(1+eeSM)]＝171.
实施例20
卤代芳烃III为4-N,N-二甲基胺溴苯，34.0mg,43％yield,91％ee.分析数据:[α]D 29＝+78.6(c＝0.1丙酮).1H NMR(400MHz,CDCl3)δ8.59(ddd,J＝4.8,1.6,0.8Hz,1H),7.50(td,J＝8.0,2.0Hz,1H),7.45(dt,J＝8.0,1.2Hz,1H),7.13-7.09(m,3H),6.58-6.55(m,2H),4.39(d,J＝2.4Hz,1H),4.31(d,J＝2.4Hz,1H),4.07(s,5H),2.92(s,6H),2.15(s,3H).13C NMR(101MHz,CDCl3)δ158.6,148.9,148.6,134.7,130.2,127.1,125.8,120.6,111.9,88.5,85.4,84.4,71.5,69.1,67.7,40.5,14.5.IR(薄膜):νmax(cm-1)＝2970,2919,1611,1585,1527,1480,1453,1430,1408,1376,1347,1225,1195,1165,1147,1103,1054,1012,946,892,812,789,745,682,659,640,612.HRMS(ESI)计算值C24H25[56Fe]N2[M+H]+:397.1362.实测值:397.1361.手性柱Daicel Chiralcel OD-H(4.6×250mm),正己烷/异丙醇＝90/10,1.0mL/min,λ＝254nm,t(minor)＝6.90min,t(major)＝7.62min.
II-1.深红色液体,24.4mg,44％yield,86％ee.eeSM＝85.74％；eePR＝91.44％；Calculated conversion,C＝eeSM/(eeSM+eePR)＝48％；Selectivity(s)＝ln[(1-C)(1-eeSM)]/ln[(1-C)(1+eeSM)]＝62.
实施例21
卤代芳烃III为对苯基溴苯，38.6mg,45％yield,94％ee.分析数据:[α]D 29＝+82.9(c＝0.1丙酮).1H NMR(400MHz,CDCl3)δ8.60(ddd,J＝4.8,1.6,0.8Hz,1H),7.59-7.56(m,2H),7.53(td,J＝8.0,2.0Hz,1H),7.47(d,J＝8.0Hz,1H),7.43-7.37(m,4H),7.34-7.28(m,2H),7.26(d,J＝8.0Hz,1H),7.14(ddd,J＝7.2,4.8,1.2Hz,1H),4.51(d,J＝2.8Hz,1H),4.39(d,J＝2.8Hz,1H),4.11(s,5H),2.16(s,3H).13C NMR(101MHz,CDCl3)δ158.1,148.8,140.9,138.6,137.7,134.9,129.8,128.7,127.0,127.0,126.8,126.3,120.9,87.1,86.0,85.2,71.7,69.7,68.3,14.4.IR(薄膜):νmax(cm-1)＝2970,2919,2852,1645,1601,1584,1558,1527,1481,1448,1430,1407,1394,1376,1318,1255,1187,1161,1146,1101,1077,1052,1000,913,894,843,819,789,764,747,730,701,643,628,608.HRMS(ESI)计算值C28H24[56Fe]N[M+H]+:430.1253.实测值:430.1254.手性柱Daicel Chiralcel OD-H(4.6×250mm),正己烷/异丙醇＝90/10,1.0mL/min,λ＝254nm,t(major)＝6.11min,t(minor)＝6.77min.
II-1.深红色液体,22.0mg,40％yield,99％ee.eeSM＝98.86％；eePR＝93.90％；Calculated conversion,C＝eeSM/(eeSM+eePR)＝51％；Selectivity(s)＝ln[(1-C)(1-eeSM)]/ln[(1-C)(1+eeSM)]＝163.
实施例22
卤代芳烃III为对氟溴苯，33.4mg,45％yield,93％ee.分析数据:[α]D 29＝+24.3(c＝0.1丙酮).1H NMR(400MHz,CDCl3)δ8.59(ddd,J＝4.8,2.0,1.2Hz,1H),7.53(td,J＝7.6,1.6Hz,1H),7.41(dt,J＝8.0,1.2Hz,1H),7.21-7.17(m,2H),7.13(ddd,J＝7.6,4.8,1.2Hz,1H),6.88-6.82(m,2H),4.44(d,J＝2.4Hz,1H),4.36(d,J＝2.4Hz,1H),4.08(s,5H),2.14(s,3H).13C NMR(101MHz,CDCl3)δ161.4(J＝245.9Hz),157.8,148.8,134.92,134.2(J＝3.2Hz),130.8(J＝7.9Hz),126.8,120.9,114.5(J＝21.3Hz),86.8,86.0,85.0,71.6,69.5,68.1,14.4.19F NMR(377MHz,CDCl3)δ-116.8(m).IR(薄膜):νmax(cm-1)＝2973,2917,1610,1582,1563,1481,1448,1430,1411,1376,1298,1262,1197,1177,1152,1104,1080,1053,1001,965,945,872,838,816,784,736,695,677,640,614.HRMS(ESI)计算值C22H19[56Fe]NF[M+H]+:372.0846.实测值:372.0857.手性柱Daicel Chiralcel OD-H(4.6×250mm),正己烷/异丙醇＝95/05,1.0mL/min,λ＝254nm,t(major)＝5.26min,t(minor)＝5.80min.
II-1.深红色液体,33.4mg,45％yield,93％ee.eeSM＝92.90％；eePR＝93.10％；Calculated conversion,C＝eeSM/(eeSM+eePR)＝50％；Selectivity(s)＝ln[(1-C)(1-eeSM)]/ln[(1-C)(1+eeSM)]＝95.
实施例23
卤代芳烃III为对乙酰基溴苯，39.5mg,50％yield,80％ee.分析数据:[α]D 29＝+31.1(c＝0.1丙酮).1H NMR(400MHz,CDCl3)δ8.59(ddd,J＝4.8,1.6,0.8Hz,1H),7.75-7.71(m,2H),7.56(td,J＝7.6,1.6Hz,1H),7.44(dt,J＝7.6,0.8Hz,1H),7.29-7.26(m,2H),7.16(ddd,J＝7.6,5.2,1.2Hz,1H),4.55(d,J＝2.4Hz,1H),4.43(d,J＝2.4Hz,1H),4.09(s,5H),2.55(s,3H),2.13(s,3H).13C NMR(101MHz,CDCl3)δ197.7,157.5,149.0,144.9,135.1,134.6,129.1,127.7,126.8,121.1,86.7,86.0,85.3,71.9,70.2,68.3,26.5,14.2.IR(薄膜):νmax(cm-1)＝2972,2903,1676,1600,1585,1561,1481,1429,1410,1395,1377,1356,1303,1265,1182,1148,1104,1053,1012,955,912,816,789,732,700,679,636.HRMS(ESI)计算值C24H22[56Fe]NO[M+H]+:396.1045.实测值:396.1047.手性柱Daicel Chiralcel OD-H(4.6×250mm),正己烷/异丙醇＝90/10,1.0mL/min,λ＝254nm,t(minor)＝10.22min,t(major)＝11.65min.
II-1.深红色液体,22.2mg,40％yield,>99％ee.eeSM＝99.88％；eePR＝79.98％；Calculated conversion,C＝eeSM/(eeSM+eePR)＝56％；Selectivity(s)＝ln[(1-C)(1-eeSM)]/ln[(1-C)(1+eeSM)]＝64.
实施例24
卤代芳烃III为3-甲氧基溴苯，35.2mg,46％yield,94％ee.分析数据:[α]D 29＝+57.7(c＝0.1丙酮).1H NMR(400MHz,CDCl3)δ8.59(ddd,J＝4.8,2.0,0.8Hz,1H),7.52(td,J＝8.0,2.0Hz,1H),7.44(dt,J＝7.6,0.8Hz,1H),7.13(ddd,J＝7.2,4.8,1.2Hz,1H),7.10-7.05(m,1H),6.84(dt,J＝7.6,0.8Hz,1H),6.77-6.75(m,1H),6.70(ddd,J＝8.0,2.4,0.8Hz,1H),4.48(d,J＝2.4Hz,1H),4.36(d,J＝2.4Hz,1H),4.09(s,5H),3.63(s,3H),2.15(s,3H).13C NMR(101MHz,CDCl3)δ158.7,158.1,148.7,140.0,134.8,128.5,127.1,122.1,120.8,114.9,111.8,87.6,86.0,85.0,71.7,69.5,68.4,54.9,14.4.IR(薄膜):νmax(cm-1)＝2966,2903,1609,1585,1562,1518,1481,1454,1432,1407,1320,1299,1270,1243,1175,1148,1104,1033,1000,905,830,813,786,746,699,677,620.HRMS(ESI)计算值C23H22[56Fe]NO[M+H]+:384.1045.实测值:384.1054.手性柱Daicel Chiralcel OD-H(4.6×250mm),正己烷/异丙醇＝95/05,1.0mL/min,λ＝254nm,t(major)＝7.74min,t(minor)＝11.00min.
II-1.深红色液体,24.0mg,43％yield,99％ee.eeSM＝98.88％；eePR＝92.70％；Calculated conversion,C＝eeSM/(eeSM+eePR)＝52％；Selectivity(s)＝ln[(1-C)(1-eeSM)]/ln[(1-C)(1+eeSM)]＝136.
实施例25
卤代芳烃III为3-氟溴苯，34.9mg,47％yield,85％ee.分析数据:[α]D 29＝+21.0(c＝0.1丙酮).1H NMR(400MHz,CDCl3)δ8.59(ddd,J＝4.8,1.6,0.8Hz,1H),7.55(td,J＝7.6,1.6Hz,1H),7.44(dt,J＝7.6,0.8Hz,1H),7.15(ddd,J＝7.6,4.8,1.2Hz,1H),7.08(dd,J＝8.0,6.0Hz,1H),6.98-6.92(m,2H),6.83(tdd,J＝8.4,2.4,1.2Hz,1H),4.48(d,J＝2.4Hz,1H),4.38(d,J＝2.4Hz,1H),4.10(s,5H),2.13(s,3H).13C NMR(101MHz,CDCl3)δ162.2(J＝245.4Hz),157.6,148.9,141.3(J＝8.2Hz),135.0,128.9(J＝8.5Hz),126.8,125.0(J＝2.6Hz),121.1,116.0(J＝22.0Hz),112.7(J＝21.3Hz),86.2,86.1(J＝2.3Hz),85.4,71.8,69.7,68.2,14.3.19F NMR(377MHz,CDCl3)δ-114.3(m).IR(薄膜):νmax(cm-1)＝2973,2917,1610,1582,1563,1481,1448,1430,1411,1376,1298,1262,1197,1177,1152,1104,1080,1053,1001,965,945,872,838,816,784,736,695,677,640,614.HRMS(ESI)计算值C22H19[56Fe]NF[M+H]+:372.0846.实测值:372.0844.手性柱Daicel Chiralcel OD-H(4.6×250mm),正己烷/异丙醇＝95/05,0.7mL/min,λ＝254nm,t(major)＝7.39min,t(minor)＝7.80min.
II-1.深红色液体,24.4mg,44％yield,96％ee.eeSM＝96.46％；eePR＝84.68％；Calculated conversion,C＝eeSM/(eeSM+eePR)＝53％；Selectivity(s)＝ln[(1-C)(1-eeSM)]/ln[(1-C)(1+eeSM)]＝48.
实施例26
卤代芳烃III为2-溴萘，32.1mg,40％yield,93％ee.分析数据:[α]D 29＝+64.2(c＝0.1丙酮).1H NMR(400MHz,CDCl3)δ8.61(ddd,J＝4.8,1.6,0.8Hz,1H),7.78-7.73(m,1H),7.66-7.60(m,3H),7.48(td,J＝8.0,2.0Hz,1H),7.44-7.39(m,3H),7.35(dd,J＝8.4,1.6Hz,1H),7.14(ddd,J＝7.2,4.8,1.2Hz,1H),4.60(d,J＝2.4Hz,1H),4.42(d,J＝2.3Hz,1H),4.12(s,5H),2.18(s,3H).13C NMR(101MHz,CDCl3)δ158.1,148.8,136.2,134.9,133.1,132.0,128.4,127.6,127.5,127.2,127.0,126.8,125.9,125.3,120.9,87.3,86.2,85.5,71.7,69.8,68.2,14.4.IR(薄膜):νmax(cm-1)＝2985,2916,1583,1561,1505,1480,1453,1429,1407,1376,1266,1147,1103,1053,1000,892,858,813,787,745,677,652,614.HRMS(ESI)计算值C26H22[56Fe]N[M+H]+:404.1096.实测值:404.1098.手性柱Daicel ChiralcelOD-H(4.6×250mm),正己烷/异丙醇＝95/05,1.0mL/min,λ＝254nm,t(major)＝6.62min,t(major)＝7.41min.
II-1.深红色液体,25.0mg,45％yield,69％ee.eeSM＝68.88％；eePR＝93.14％；Calculated conversion,C＝eeSM/(eeSM+eePR)＝43％；Selectivity(s)＝ln[(1-C)(1-eeSM)]/ln[(1-C)(1+eeSM)]＝58.
实施例27
卤代芳烃III为35.7mg,45％yield,98％ee.分析数据:[α]D 29＝+16.9(c＝0.1丙酮).1H NMR(400MHz,CDCl3)δ8.58(d,J＝4.0Hz,1H),7.53(td,J＝8.0,2.0Hz,1H),7.46(d,J＝7.6Hz,1H),7.12(ddd,J＝7.2,4.8,1.2Hz,1H),6.82(s,1H),6.64-6.62(m,2H),4.40(d,J＝2.4Hz,1H),4.32(d,J＝2.4Hz,1H),4.22(s,2H),4.08(s,5H),2.13(s,3H).13CNMR(101MHz,CDCl3)δ158.1,148.7,142.6,141.9,134.8,131.6,126.9,122.7,120.8,118.0,116.3,87.5,85.7,84.7,71.6,69.3,68.0,64.3,14.4.IR(薄膜):νmax(cm-1)＝2973,2900,1584,1561,1504,1481,1452,1408,1376,1342,1298,1239,1219,1185,1147,1104,1037,933,859,809,788,735,700,657,638,615.HRMS(ESI)计算值C23H20[56Fe]NO2[M+H]+:398.0838.实测值:398.0833.手性柱Daicel Chiralcel OD-H(4.6×250mm),正己烷/异丙醇＝90/10,1.0mL/min,λ＝254nm,t(minor)＝7.81min,t(major)＝10.43min.
II-1.深红色液体,25.4mg,46％yield,>99％ee.eeSM＝99.66％；eePR＝97.72％；Calculated conversion,C＝eeSM/(eeSM+eePR)＝50％；Selectivity(s)＝ln[(1-C)(1-eeSM)]/ln[(1-C)(1+eeSM)]＝552.
实施例28
卤代芳烃III为37.8mg,46％yield,97％ee.分析数据:[α]D 29＝+61.1(c＝0.1丙酮).1H NMR(400MHz,CDCl3)δ8.59-8.56(m,1H),7.52(td,J＝7.6,1.6Hz,1H),7.45(d,J＝8.0Hz,1H),7.12(ddd,J＝7.6,5.2,1.2Hz,1H),6.82(s,1H),6.62(d,J＝1.2Hz,2H),4.39(d,J＝2.4Hz,1H),4.31(d,J＝2.4Hz,1H),4.21(s,4H),4.07(s,5H),2.13(s,3H).13CNMR(101MHz,CDCl3)δ158.1,148.7,142.6,141.9,134.8,131.6,126.9,122.7,120.8,118.0,116.3,87.5,85.7,84.7,71.6,69.3,68.0,64.3,14.4.IR(薄膜):νmax(cm-1)＝2973,2919,1582,1562,1513,1482,1457,1441,1411,1377,1338,1299,1278,1252,1221,1193,1175,1148,1123,1103,1065,1001,925,888,845,811,788,745,699,664,638,615.HRMS(ESI)计算值C24H22[56Fe]NO2[M+H]+:412.0995.实测值:412.0999.手性柱Daicel ChiralcelOD-3(4.6×250mm),正己烷/异丙醇＝85/15,1.0mL/min,λ＝254nm,t(minor)＝6.91min,t(major)＝25.15min.
II-1.深红色液体,25.1mg,45％yield,99％ee.eeSM＝98.88％；eePR＝97.36％；Calculated conversion,C＝eeSM/(eeSM+eePR)＝50％；Selectivity(s)＝ln[(1-C)(1-eeSM)]/ln[(1-C)(1+eeSM)]＝388.
实施例29
卤代芳烃III为33.7mg,47％yield,94％ee.分析数据:[α]D 29＝+1.9(c＝0.1丙酮).1H NMR(400MHz,CDCl3)δ8.62-8.60(m,1H),7.57(td,J＝8.0,2.0Hz,1H),7.54-7.51(m,1H),7.18-7.12(m,2H),6.92-6.87(m,2H),4.46(d,J＝2.4Hz,1H),4.33(d,J＝2.4Hz,1H),4.09(s,5H),2.11(s,3H).13C NMR(101MHz,CDCl3)δ157.9,148.8,138.7,135.0,129.0,126.8,124.2,121.0,120.8,86.2,84.9,81.9,71.5,69.4,67.5,14.3.IR(薄膜):νmax(cm-1)＝3064,2971,2917,2349,1705,1583,1562,1543,1518,1482,1449,1408,1375,1308,1291,1255,1204,1158,1102,1078,1040,1016,999,986,931,905,846,816,784,748,731,698,667,643,614.HRMS(ESI)计算值C20H18[56Fe]NS[M+H]+:360.0504.实测值:360.0508.手性柱Daicel Chiralpak AD-H(4.6×250mm),正己烷/异丙醇＝90/10,1.0mL/min,λ＝254nm,t(major)＝4.68min,t(minor)＝7.14min.
II-1.深红色液体,23.9mg,43％yield,>99％ee.eeSM＝99.80％；eePR＝93.50％；Calculated conversion,C＝eeSM/(eeSM+eePR)＝52％；Selectivity(s)＝ln[(1-C)(1-eeSM)]/ln[(1-C)(1+eeSM)]＝203.
实施例30
卤代芳烃III为32.8mg,40％yield,98％ee.分析数据:[α]D 29＝+153.9(c＝0.1丙酮).1H NMR(400MHz,CDCl3)δ8.60(ddd,J＝4.8,1.6,0.8Hz,1H),7.69(d,J＝1.6Hz,1H),7.63(d,J＝8.4Hz,1H),7.48(td,J＝7.6,1.6Hz,1H),7.43-7.37(m,2H),7.23-7.19(m,2H),7.12(ddd,J＝7.2,4.8,1.2Hz,1H),4.53(d,J＝2.4Hz,1H),4.39(d,J＝2.4Hz,1H),4.11(s,5H),2.18(s,3H).13C NMR(101MHz,CDCl3)δ158.1,148.8,139.4,137.5,134.8,134.6,127.0,126.6,126.4,123.9,123.8,121.4,120.9,87.8,86.0,85.1,71.7,69.6,68.4,14.4.IR(薄膜):νmax(cm-1)＝2985,2902,1583,1561,1510,1481,1452,1429,1406,1377,1311,1259,1188,1172,1148,1103,1046,1001,944,893,808,787,734,700,658,634,614.HRMS(ESI)计算值C24H20[56Fe]NS[M+H]+:410.0660.实测值:410.0659.手性柱DaicelChiralpak IG(4.6×250mm),正己烷/异丙醇＝90/10,1.0mL/min,λ＝254nm,t(major)＝8.14min,t(minor)＝15.57min.
II-1.深红色液体,26.6mg,48％yield,83％ee.eeSM＝83.14％；eePR＝98.14％；Calculated conversion,C＝eeSM/(eeSM+eePR)＝46％；Selectivity(s)＝ln[(1-C)(1-eeSM)]/ln[(1-C)(1+eeSM)]＝279.
实施例31
卤代芳烃III为36.2mg,46％yield,98％ee.分析数据:[α]D 29＝-4.6(c＝0.1丙酮).1H NMR(400MHz,CDCl3)δ8.59(ddd,J＝4.8,1.6,0.8Hz,1H),7.57(d,J＝2.0Hz,1H),7.50-7.44(m,2H),7.39(d,J＝8.0Hz,1H),7.28(d,J＝8.8Hz,1H),7.18(dd,J＝8.4,1.6Hz,1H),7.12(ddd,J＝7.2,4.8,1.2Hz,1H),6.66(dd,J＝2.0,0.8Hz,1H),4.48(d,J＝2.4Hz,1H),4.37(d,J＝2.4Hz,1H),4.10(s,5H),2.18(s,3H).13C NMR(101MHz,CDCl3)δ158.2,153.7,148.7,145.1,134.8,132.8,127.0,126.5,121.7,120.8,110.3,106.5,88.5,85.9,84.8,71.7,69.4,68.5,14.5.IR(薄膜):νmax(cm-1)＝2972,2918,1584,1561,1479,1432,1375,1325,1258,1223,1186,1149,1131,1106,1054,1030,1000,890,859,810,789,769,735,701,641,616.HRMS(ESI)计算值C24H20[56Fe]NO[M+H]+:394.0889.实测值:394.0893.手性柱Daicel Chiralpak AD-H(4.6×250mm),正己烷/异丙醇＝90/10,1.0mL/min,λ＝254nm,t(major)＝5.05min,t(minor)＝7.21min.
II-1.深红色液体,25.4mg,46％yield,99％ee.eeSM＝98.82％；eePR＝97.78％；Calculated conversion,C＝eeSM/(eeSM+eePR)＝50％；Selectivity(s)＝ln[(1-C)(1-eeSM)]/ln[(1-C)(1+eeSM)]＝458.
实施例32
卤代芳烃III为52.4mg,48％yield,95％ee.分析数据:[α]D 29＝+100.2(c＝0.1丙酮).1H NMR(400MHz,CDCl3)δ8.58-8.55(m,1H),7.78-7.72(m,3H),7.51-7.43(m,2H),7.39-7.35(m,2H),7.23(d,J＝8.0Hz,2H),7.18(dd,J＝8.8,1.6Hz,1H),7.12(ddd,J＝7.2,4.8,1.2Hz,1H),6.51(d,J＝3.6Hz,1H),4.44(d,J＝2.4Hz,1H),4.35(d,J＝2.4Hz,1H),4.07(s,5H),2.35(s,3H),2.15(s,3H).13C NMR(101MHz,CDCl3)δ158.0,148.7,144.9,135.4,134.8,133.5,133.3,130.4,129.8,127.0,126.9,126.7,126.3,121.7,120.8,112.5,108.9,88.0,85.9,84.9,71.7,69.5,68.4,21.6,14.5.IR(薄膜):νmax(cm-1)＝2985,2903,1584,1477,1444,1405,1377,1359,1307,1255,1192,1164,1126,1078,1055,995,935,913,895,873,816,791,766,748,722,697,671,646,605.HRMS(ESI)计算值C31H27[56Fe]N2O2S[M+H]+:547.1137.实测值:547.1138.HPLC:手性柱Daicel Chiralcel OD-H(4.6×250mm),正己烷/异丙醇＝90/10,1.0mL/min,λ＝254nm,t(minor)＝13.17min,t(major)＝14.41min.
II-1.深红色液体,23.8mg,43％yield,>99％ee.eeSM＝99.70％；eePR＝95.20％；Calculated conversion,C＝eeSM/(eeSM+eePR)＝51％；Selectivity(s)＝ln[(1-C)(1-eeSM)]/ln[(1-C)(1+eeSM)]＝262.
实施例33
卤代芳烃III为33.4mg,40％yield,96％ee.分析数据:[α]D 29＝+30.5(c＝0.1丙酮).1H NMR(400MHz,CDCl3)δ8.59(ddd,J＝4.8,1.6,0.8Hz,1H),7.83(d,J＝8.4Hz,1H),7.79(d,J＝8.8Hz,1H),7.57(dd,J＝8.8,2.0Hz,1H),7.52(d,J＝2.0Hz,1H),7.51-7.47(m,1H),7.43(dt,J＝8.0,1.2Hz,1H),7.21(d,J＝8.4Hz,1H),7.14(ddd,J＝7.2,4.8,1.2Hz,1H),4.59(d,J＝2.4Hz,1H),4.43(d,J＝2.4Hz,1H),4.12(s,5H),2.70(s,3H),2.17(s,3H).13C NMR(101MHz,CDCl3)δ158.3,157.8,148.9,146.6,136.3,135.8,135.0,131.9,127.4,126.9,126.6,126.1,122.1,121.0,86.5,86.3,85.6,71.7,69.9,68.1,25.2,14.3.IR(薄膜):νmax(cm-1)＝2970,2919,1584,1561,1479,1452,1430,1408,1374,1311,1244,1222,1148,1121,1103,1053,1001,934,889,836,813,788,746,699,663,613.HRMS(ESI)计算值C26H23[56Fe]N2[M+H]+:419.1205.实测值:419.1213.手性柱Daicel ChiralpakIG(4.6×250mm),正己烷/异丙醇＝85/05,1.0mL/min,λ＝254nm,t(major)＝12.78min,t(minor)＝19.82min.
II-1.深红色液体,28.3mg,51％yield,71％ee.eeSM＝71.02％；eePR＝96.48％；Calculated conversion,C＝eeSM/(eeSM+eePR)＝42％；Selectivity(s)＝ln[(1-C)(1-eeSM)]/ln[(1-C)(1+eeSM)]＝119.
实施例34
卤代芳烃III为对甲氧基溴苯，34.3mg,43％yield,94％ee.分析数据:[α]D 27＝+75.3(c＝0.1丙酮).1H NMR(400MHz,CD2Cl2)δ8.5(dd,J＝4.0,0.8Hz,1H),7.55(td,J＝7.7,1.6Hz,1H),7.47(dt,J＝8.0,1.2Hz,1H),7.16-7.12(m,3H),6.71(d,J＝8.8Hz,2H),4.38(d,J＝2.4Hz,1H),4.22(d,J＝2.4Hz,1H),3.99-3.97(m,1H),3.96-3.93(m,2H),3.90-3.88(m,1H),3.77(s,3H),2.08(s,3H),1.85(s,3H).13C NMR(101MHz,CD2Cl2)δ159.0,158.7,149.5,135.6,131.2,131.1,127.7,121.5,113.8,88.1,86.3,85.64,85.57,73.3,73.0,72.24,72.20,71.4,69.3,55.9,14.4,14.0.IR(薄膜):νmax(cm-1)＝2949,2905,2871,2834,1610,1586,1561,1519,1478,1459,1430,1415,1387,1296,1260,1241,1197,1175,1138,1105,1075,1033,1003,967,950,815,787,722,693.HRMS(ESI)计算值C24H24[56Fe]NO[M+H]+:398.1202.实测值:398.1197.手性柱Daicel Chiralcel OD-H(4.6×250mm),Hexanes/EtOH＝98/02,0.7mL/min,λ＝286nm,t(minor)＝18.74min,t(major)＝20.88min.
26.0mg,45％yield,87％ee.分析数据:[α]D 27＝-86.9(c＝0.1丙酮).1H NMR(400MHz,CD2Cl2)δ8.52-8.50(m,1H),7.61(td,J＝8.0,2.0Hz,1H),7.55(dt,J＝7.6,0.8Hz,1H),7.09(ddd,J＝7.6,4.8,1.2Hz,1H),4.64(dd,J＝2.4,1.6Hz,1H),4.21-4.19(m,1H),4.19-4.17(m,1H),3.91-3.89(m,1H),3.88-3.85(m,3H),2.34(s,3H),1.76(s,3H).13C NMR(101MHz,CD2Cl2)δ160.8,149.6,136.3,122.7,120.9,85.6,84.1,83.8,73.9,71.94,71.89,70.4,70.2,70.1,68.7,15.8,13.9.IR(薄膜):νmax(cm-1)＝3079,2946,2916,1584,1562,1488,1448,1427,1415,1375,1290,1265,1226,1150,1088,1068,1036,1002,984,954,921,807,784,739,708,645,619.HRMS(ESI)计算值C17H18[56Fe]N[M+H]+:292.0783.实测值:292.0785.手性柱Daicel Chiralpak IB-N-3(4.6×250mm),正己烷/异丙醇＝90/10,0.6mL/min,λ＝286nm,t(minor)＝10.77min,t(major)＝14.49min.eeSM＝86.62％；eePR＝93.88％；Calculated conversion,C＝eeSM/(eeSM+eePR)＝52％；Selectivity(s)＝ln[(1-C)(1-eeSM)]/ln[(1-C)(1+eeSM)]＝89.
实施例35
卤代芳烃III为对甲氧基溴苯，40.5mg,46％yield,92％ee.分析数据:[α]D 26＝+72.0(c＝0.1丙酮).1H NMR(400MHz,CD2Cl2)δ8.55(dd,J＝4.8,0.8Hz,1H),7.55(td,J＝7.6,2.0Hz,1H),7.46(dt,J＝8.0,1.2Hz,1H),7.16-7.11(m,3H),6.71(d,J＝8.8Hz,2H),4.38(d,J＝2.4Hz,1H),4.22(d,J＝2.4Hz,1H),3.99-3.97(m,1H),3.97-3.94(m,1H),3.95-3.92(m,1H),3.91-3.89(m,1H),3.77(s,3H),2.23(dd,J＝8.0,6.8Hz,2H),2.08(s,3H),1.44-1.36(m,2H),1.33-1.23(m,2H),0.88(t,J＝7.2Hz,3H).13C NMR(101MHz,CD2Cl2)δ159.0,158.7,149.5,135.6,131.3,131.1,127.7,121.5,113.8,91.0,88.0,86.3,85.6,73.1,72.5,72.3,71.33,71.28,69.2,55.9,34.3,28.9,23.4,14.53,14.51.IR(薄膜):νmax(cm-1)＝2956,2919,2897,2858,2833,1609,1585,1563,1519,1479,1453,1429,1391,1360,1296,1242,1173,1105,1075,1051,1030,1001,951,899,817,785,741,707.HRMS(ESI)计算值C27H30[56Fe]NO[M+H]+:440.1671.实测值:440.1667.手性柱Daicel Chiralpak IB-N-3(4.6×250mm),正己烷/异丙醇＝95/05,0.6mL/min,λ＝286nm,t(minor)＝9.78min,t(major)＝12.00min.
27.4mg,41％yield,98％ee.分析数据:[α]D 27＝-123.5(c＝0.1丙酮).1H NMR(400MHz,CD2Cl2)δ8.51(dd,J＝4.0,1.2Hz,1H),7.61(td,J＝8.0,1.6Hz,1H),7.54(dt,J＝8.0,1.2Hz,1H),7.08(ddd,J＝7.2,4.8,1.2Hz,1H),4.64(dd,J＝2.4,1.6Hz,1H),4.20(t,J＝2.4Hz,1H),4.17(t,J＝2.4Hz,1H),3.90-3.86(m,4H),2.34(s,3H),2.13(dd,J＝8.4,6.8Hz,2H),1.40-1.32(dq,J＝8.8,7.3Hz,2H),1.30-1.20(m,2H),0.86(t,J＝7.2Hz,3H).13C NMR(101MHz,CD2Cl2)δ160.9,149.6,136.2,122.7,120.9,91.1,84.1,83.8,73.8,70.89,70.85,70.5,70.3,70.1,68.6,34.1,28.9,23.4,15.9,14.5.IR(薄膜):νmax(cm-1)＝2951,2925,2858,2833,1607,1584,1560,1516,1480,1454,1429,1396,1374,1299,1284,1241,1172,1148,1099,1078,1060,1030,1009,912,832,814,786,746,729.HRMS(ESI)计算值C20H24[56Fe]N[M+H]+:334.1253.实测值:334.1257.手性柱Daicel Chiralcel OD-H(4.6×250mm),正己烷/异丙醇＝90/10,0.7mL/min,λ＝286nm,t(minor)＝9.07min,t(major)＝13.74min.eeSM＝98.38％；eePR＝92.34％；Calculated conversion,C＝eeSM/(eeSM+eePR)＝52％；Selectivity(s)＝ln[(1-C)(1-eeSM)]/ln[(1-C)(1+eeSM)]＝120.
实施例36
卤代芳烃III为对甲氧基溴苯，39.1mg,46％yield,93％ee.分析数据:[α]D 29＝+17.5(c＝0.1丙酮).1H NMR(400MHz,CDCl3)δ8.57(d,J＝3.6Hz,1H),7.52-7.48(m,1H),7.41(d,J＝7.6Hz,1H),7.14-7.09(m,3H),6.70(d,J＝8.4Hz,2H),4.43(s,1H),4.27(s,1H),4.05(s,1H),3.99(s,1H),3.93(s,2H),3.78(s,3H),2.64-2.56(m,1H),2.10(s,3H),1.15-1.12(d,J＝6.8Hz,6H).13C NMR(101MHz,CDCl3)δ158.3,157.8,148.7,134.7,130.5,130.4,126.8,120.7,113.0,97.6,87.5,85.3,84.9,73.1,72.7,70.9,69.6,68.7,68.6,55.1,27.0,23.7,23.6,14.2.IR(薄膜):νmax(cm-1)＝2957,2922,2868,2835,1609,1584,1562,1518,1480,1455,1431,1395,1376,1301,1282,1243,1175,1148,1103,1076,1033,988,958,914,826,787,746,688,675,638,610.HRMS(ESI)计算值C26H28[56Fe]NO[M+H]+:426.1515.实测值:426.1516.手性柱Daicel Chiralcel OD-H(4.6×250mm),Hexanes/EtOH＝70/30,0.5mL/min,λ＝254nm,t(minor)＝7.92min,t(major)＝8.67min.
27.4mg,43％yield,>99％ee.分析数据:[α]D 29＝-74.9(c＝0.1丙酮).1H NMR(400MHz,CDCl3)δ8.53(d,J＝4.4Hz,1H),7.59(td,J＝8.0,1.6Hz,1H),7.53(d,J＝7.6Hz,1H),7.09-7.05(m,1H),4.67(s,1H),4.22(s,1H),4.18(t,J＝2.4Hz,1H),3.94(s,1H),3.92(s,1H),3.88(s,1H),3.83(s,1H),2.58-2.50(m,1H),2.34(s,3H),1.10(d,J＝6.8Hz,6H).13C NMR(101MHz,CDCl3)δ160.1,148.9,135.4,122.1,120.2,97.4,83.2,72.8,70.5,70.1,69.1,67.9,67.8,27.0,23.6,23.5,15.3.IR(薄膜):νmax(cm-1)＝3084,2957,2921,2867,1584,1562,1488,1449,1415,1377,1359,1293,1265,1235,1215,1149,1067,1034,1003,985,954,918,821,784,740,708,646,618.HRMS(ESI)计算值C19H22[56Fe]N[M+H]+:320.1096.实测值:320.1098.手性柱Daicel Chiralcel OD-H(4.6×250mm),正己烷/异丙醇＝70/30,0.7mL/min,λ＝254nm,t(minor)＝7.50min,t(major)＝9.99min.eeSM＝99.72％；eePR＝93.44％；Calculated conversion,C＝eeSM/(eeSM+eePR)＝52％；Selectivity(s)＝ln[(1-C)(1-eeSM)]/ln[(1-C)(1+eeSM)]＝192.
实施例37
卤代芳烃III为对甲氧基溴苯，39.8mg,47％yield,98％ee.分析数据:[α]D 29＝+18.1(c＝0.1丙酮).1H NMR(400MHz,CDCl3)δ8.58(d,J＝4.0Hz,1H),7.53-7.48(m,1H),7.38(d,J＝8.0Hz,1H),7.16-7.10(m,3H),6.71(d,J＝8.8Hz,2H),5.11(s,1H),4.90(s,1H),4.36(d,J＝2.4Hz,1H),4.30(s,1H),4.27(s,1H),4.18(d,J＝2.4Hz,1H),4.12(s,1H),4.04(s,1H),3.78(s,3H),2.07(s,3H),1.94(s,3H).13C NMR(101MHz,CDCl3)δ157.9,148.7,140.3,134.8,130.4,130.1,126.9,120.8,113.1,109.2,87.8,87.3,85.3,84.9,74.4,73.2,71.6,69.5,69.3,67.8,55.2,21.5,13.2.IR(薄膜):νmax(cm-1)＝3080,2969,2916,2834,1609,1585,1562,1518,1481,1452,1431,1375,1338,1285,1243,1175,1149,1103,1077,1032,934,913,874,826,787,746,701,660,638,611.HRMS(ESI)计算值C26H26[56Fe]NO[M+H]+:424.1358.实测值:424.1364.手性柱Daicel Chiralpak AD-H(4.6×250mm),正己烷/异丙醇＝80/20,0.7mL/min,λ＝254nm,t(major)＝6.00min,t(minor)＝10.84min.
25.5mg,40％yield,>99％ee.分析数据:[α]D 29＝-105.0(c＝0.1丙酮).1H NMR(400MHz,CDCl3)δ8.53(d,J＝4.0Hz,1H),7.62-7.57(m,1H),7.49(d,J＝8.0Hz,1H),7.09-7.05(m,1H),5.03(s,1H),4.83(s,1H),4.66-4.64(m,1H),4.21(s,1H),4.17(s,3H),4.08(s,2H),2.27(s,3H),1.88(s,3H).13C NMR(101MHz,CDCl3)δ159.5,148.9,140.3,135.4,122.2,120.3,108.8,87.2,83.6,83.4,73.6,71.3,71.0,69.9,68.5,68.1,67.5,21.4,14.4.IR(薄膜):νmax(cm-1)＝3082,2970,2917,1625,1585,1562,1488,1449,1428,1415,1375,1291,1264,1215,1149,1066,1036,1002,985,955,937,871,814,784,740,708,645,618.HRMS(ESI)计算值C19H20[56Fe]N[M+H]+:318.0940.实测值:318.0949.手性柱DaicelChiralcel OD-H(4.6×250mm),正己烷/异丙醇＝70/30,0.7mL/min,λ＝254nm,t(minor)＝9.92min,t(major)＝10.95min.eeSM＝99.56％；eePR＝97.82％；Calculated conversion,C＝eeSM/(eeSM+eePR)＝50％；Selectivity(s)＝ln[(1-C)(1-eeSM)]/ln[(1-C)(1+eeSM)]＝554.
实施例38
卤代芳烃III为对甲氧基溴苯，41.2mg,45％yield,97％ee.分析数据:[α]D 27＝-42.9(c＝0.1丙酮).1H NMR(400MHz,CD2Cl2)δ8.57(dd,J＝4.8,0.8Hz,1H),7.56(td,J＝7.6,2.0Hz,1H),7.42(dt,J＝8.0,1.2Hz,1H),7.18-7.12(m,3H),6.71(d,J＝8.8Hz,2H),4.41(d,J＝2.4Hz,1H),4.31(d,J＝2.4Hz,1H),4.21-7.18(m,1H),4.14-4.12(m,1H),4.02-3.99(m,2H),3.77(s,3H),2.10(s,3H),0.23(s,9H).13C NMR(101MHz,CD2Cl2)δ158.87,158.85,149.6,135.7,131.2,127.5,121.7,113.8,87.9,86.6,85.7,78.1,77.9,76.4,76.3,73.2,70.6,68.4,55.9,14.8,0.33.IR(薄膜):νmax(cm-1)＝2953,2916,2834,1600,1554,1518,1482,1454,1433,1374,1301,1278,1242,1175,1105,1079,1031,1000,816,792,733.HRMS(ESI)计算值C26H30[56Fe]NOSi[M+H]+:456.1441.实测值:456.1442.手性柱Daicel Chiralcel OD-H(4.6×250mm),正己烷/异丙醇＝98/02,0.7mL/min,λ＝286nm,t(minor)＝9.31min,t(major)＝11.06min.
31.2mg,45％yield,94％ee.分析数据:[α]D 23＝+10.3(c＝0.1丙酮).1H NMR(400MHz,CD2Cl2)δ8.52(dd,J＝4.8,2.0Hz,1H),7.62(td,J＝8.0,2.0Hz,1H),7.56(d,J＝8.0Hz,1H),7.11(ddd,J＝6.4,4.8,1.2Hz,1H),4.67-4.66(m,1H),4.26(t,J＝2.4Hz,1H),4.18(t,J＝2.4Hz,1H),4.07-4.05(m,1H),4.05-4.02(m,2H),3.99-3.97(m,1H),2.34(s,3H),0.21(s,9H).13C NMR(101MHz,CD2Cl2)δ160.8,149.7,136.3,122.9,121.1,84.3,84.1,75.9,75.4,75.3,75.2,73.2,72.9,69.7,68.2,16.0,0.3.IR(薄膜):νmax(cm-1)＝2951,2895,1585,1563,1489,1449,1416,1377,1245,1216,1161,1034,1003,899,824,784,742,690,647,628.HRMS(ESI)计算值C19H24[56Fe]NSi[M+H]+:350.1022.实测值:350.1031.手性柱Daicel Chiralpak IB-N-3(4.6×250mm),正己烷/异丙醇＝90/10,0.6mL/min,λ＝286nm,t(minor)＝7.34min,t(major)＝11.94min.eeSM＝93.98％；eePR＝97.46％；Calculated conversion,C＝eeSM/(eeSM+eePR)＝49％；Selectivity(s)＝ln[(1-C)(1-eeSM)]/ln[(1-C)(1+eeSM)]＝278.
实施例39
卤代芳烃III为对甲氧基溴苯，40.1mg,44％yield,95％ee.分析数据:[α]D 27＝+34.4(c＝0.1丙酮).1H NMR(400MHz,CD2Cl2)δ8.57(ddd,J＝4.8,2.0,0.8Hz,1H),7.58(td,J＝7.6,2.0Hz,1H),7.47(dt,J＝8.0,1.2Hz,1H),7.16(ddd,J＝7.6,5.2,1.2Hz,1H),7.14-7.09(m,2H),6.72-6.68(m,2H),4.40(s,1H),4.08(s,5H),3.76(s,3H),2.09(s,3H),0.37(s,9H).13C NMR(101MHz,CD2Cl2)δ158.9,158.8,149.5,135.7,131.2,131.0,127.8,121.7,113.9,90.4,90.3,90.2,74.5,72.6,72.0,55.9,15.0,0.9.IR(薄膜):νmax(cm-1)＝2951,2926,2858,2834,1608,1584,1561,1517,1481,1455,1430,1397,1373,1298,1284,1241,1173,1148,1104,1078,1031,1009,832,813,787,746,688.HRMS(ESI)计算值C26H30[56Fe]NOSi[M+H]+:456.1441.实测值:456.1435.手性柱Daicel Chiralcel OD-H(4.6×250mm),正己烷/异丙醇＝95/05,1.0mL/min,λ＝254nm,t(major)＝4.23min,t(minor)＝6.09min.
31.4mg,45％yield,81％ee.分析数据:[α]D 27＝-243.2(c＝0.1丙酮).1H NMR(400MHz,CD2Cl2)δ8.53(ddd,J＝4.8,2.0,1.2Hz,1H),7.64(td,J＝8.0,2.0Hz,1H),7.59(dt,J＝8.0,1.2Hz,1H),7.12(ddd,J＝7.2,4.8,1.2Hz,1H),4.76(d,J＝2.4Hz,1H),4.17(d,J＝2.4Hz,1H),4.01(s,5H),2.34(s,3H),0.34(s,9H).13C NMR(101MHz,CD2Cl2)δ160.6,149.6,136.3,123.7,121.2,88.9,88.2,74.7,73.9,71.8,71.2,15.8,0.8.IR(薄膜):νmax(cm-1)＝3082,2951,2897,1585,1563,1489,1449,1416,1377,1292,1245,1161,1087,1066,1034,1003,899,824,784,742,690,647,628.HRMS(ESI)计算值C19H24[56Fe]NSi[M+H]+:350.1022.实测值:350.1023.手性柱Daicel Chiralcel OD-3(SFC:3.0mm,I.D.:150mm),CO2/MeOH＝95/05,1.0mL/min,λ＝214nm,t(major)＝4.20min,t(major)＝4.52min.eeSM＝80.6％；eePR＝95.26％；Calculated conversion,C＝eeSM/(eeSM+eePR)＝46％；Selectivity(s)＝ln[(1-C)(1-eeSM)]/ln[(1-C)(1+eeSM)]＝103.
实施例40
卤代芳烃III为对甲氧基溴苯，36.5mg,46％yield,96％ee.分析数据:[α]D 26＝-142.0(c＝0.1丙酮).1H NMR(400MHz,CD2Cl2)δ8.40(d,J＝4.8Hz,1H),7.32(d,J＝1.6Hz,1H),7.13(d,J＝8.8Hz,2H),7.01-6.98(m,1H),6.70(d,J＝8.8Hz,2H),4.44(d,J＝2.4Hz,1H),4.34(d,J＝2.4Hz,1H),4.08(s,5H),3.77(s,3H),2.30(s,3H),2.07(s,3H).13C NMR(101MHz,CD2Cl2)δ158.8,158.5,149.2,146.8,131.4,131.0,128.4,122.8,113.8,88.1,87.1,85.6,72.4,69.9,68.2,55.9,21.6,14.8.IR(薄膜):νmax(cm-1)＝2954,2916,1600,1554,1519,1482,1455,1433,1411,1375,1279,1243,1176,1105,1079,1033,1001,818,792.HRMS(ESI)计算值C24H24[56Fe]NO[M+H]+:398.1202.实测值:398.1211.手性柱DaicelChiralcel OD-H(4.6×250mm),Hexanes/EtOH＝90/10,1.0mL/min,λ＝254nm,t(minor)＝5.66min,t(major)＝7.35min.
26.0mg,45％yield,94％ee.分析数据:[α]D 27＝+140.6(c＝0.1丙酮).1H NMR(400MHz,CD2Cl2)δ8.36(d,J＝5.2Hz,1H),7.39(d,J＝1.6Hz,1H),6.96-6.93(m,1H),4.65(dd,J＝2.8,1.6Hz,1H),4.27(t,J＝2.0Hz,1H),4.20(t,J＝2.8Hz,1H),4.01(s,5H),2.38(s,3H),2.33(s,3H).13C NMR(101MHz,CD2Cl2)δ160.6,149.4,147.3,123.7,122.3,84.5,84.2,72.7,71.0,69.7,67.7,21.7,16.0.IR(薄膜):νmax(cm-1)＝3089,2917,1598,1553,1487,1446,1410,1376,1293,1277,1226,1190,1103,1034,999,882,814,755,735,651.HRMS(ESI)计算值C17H18[56Fe]N[M+H]+:292.0783.实测值:292.0790.手性柱DaicelChiralcel OD-H(4.6×250mm),正己烷/异丙醇＝95/05,1.0mL/min,λ＝254nm,t(major)＝5.81min,t(minor)＝7.29min.eeSM＝93.62％；eePR＝95.70％；Calculated conversion,C＝eeSM/(eeSM+eePR)＝49％；Selectivity(s)＝ln[(1-C)(1-eeSM)]/ln[(1-C)(1+eeSM)]＝160.
实施例41
卤代芳烃III为对甲氧基溴苯，36.5mg,46％yield,95％ee.分析数据:[α]D 26＝+44.6(c＝0.1丙酮).1H NMR(400MHz,CD2Cl2)δ8.39(s,1H),7.38(s,2H),7.14(d,J＝8.8Hz,2H),6.70(d,J＝8.8Hz,2H),4.43(d,J＝2.4Hz,1H),4.34(d,J＝2.4Hz,1H),4.08(s,5H),3.77(s,3H),2.34(s,3H),2.08(s,3H).13C NMR(101MHz,CD2Cl2)δ158.8,155.7,149.8,136.4,131.4,131.2,131.1,127.1,113.8,88.3,86.8,85.6,72.4,70.0,68.4,55.9,18.8,14.9.IR(薄膜):νmax(cm-1)＝2919,2833,1608,1598,1561,1518,1493,1454,1432,1372,1300,1276,1242,1174,1104,1083,1030,1000,913,829,813,792,732,701,613.HRMS(ESI)计算值C24H24[56Fe]NO[M+H]+:398.1202.实测值:398.1199.手性柱Daicel Chiralcel OD-H(4.6×250mm),正己烷/异丙醇＝90/10,1.0mL/min,λ＝254nm,t(minor)＝6.40min,t(major)＝7.98min.
27.1mg,47％yield,90％ee.分析数据:[α]D 27＝-84.2(c＝0.1丙酮).1H NMR(400MHz,CD2Cl2)δ8.35(s,1H),7.50-7.43(m,2H),4.64(dd,J＝2.4,1.6Hz,1H),4.26(t,J＝2.0Hz,1H),4.19(t,J＝2.4Hz,1H),4.00(s,5H),2.32(s,3H),2.31(s,3H).13C NMR(101MHz,CD2Cl2)δ157.7,150.0,137.0,130.5,122.5,84.6,84.0,72.6,71.0,69.5,67.5,18.7,16.0.IR(薄膜):νmax(cm-1)＝3091,2948,2919,2866,1597,1562,1498,1451,1410,1375,1290,1265,1226,1130,1103,1056,1029,998,955,813,734,702,676,654,638.HRMS(ESI)计算值C17H18[56Fe]N[M+H]+:292.0783.实测值:292.0785.手性柱Daicel Chiralpak IG(4.6×250mm),正己烷/异丙醇＝95/05,1.0mL/min,λ＝254nm,t(minor)＝5.82min,t(major)＝6.23min.eeSM＝89.70％；eePR＝95.38％；Calculated conversion,C＝eeSM/(eeSM+eePR)＝48％；Selectivity(s)＝ln[(1-C)(1-eeSM)]/ln[(1-C)(1+eeSM)]＝130.
实施例42
卤代芳烃III为对甲氧基溴苯，32.1mg,45％yield,99％ee.分析数据:[α]D 23＝+154.6(c＝0.1丙酮).1H NMR(400MHz,CD2Cl2)δ8.62(d,J＝5.2Hz,1H),7.66(d,J＝2.0Hz,1H),7.52-7.42(m,5H),7.39(dd,J＝5.2,2.0Hz,1H),7.23(d,J＝8.8Hz,2H),6.75(d,J＝8.8Hz,2H),4.48(d,J＝2.4Hz,1H),4.39(d,J＝2.4Hz,1H),4.11(s,5H),3.78(s,3H),2.19(s,3H).13C NMR(101MHz,CD2Cl2)δ159.5,159.0,150.0,147.8,139.3,131.4,131.3,129.8,129.6,127.7,125.5,119.7,114.0,88.7,86.6,85.6,72.4,70.2,68.7,56.0,15.0.IR(薄膜):νmax(cm-1)＝2915,2833,1607,1590,1540,1518,1478,1456,1431,1363,1300,1279,1242,1174,1104,1078,1030,1000,895,830,813,760,733,695,613.HRMS(ESI)计算值C29H26[56Fe]NO[M+H]+:460.1358.实测值:460.1359.手性柱Daicel Chiralcel OD-H(4.6×250mm),正己烷/异丙醇＝90/10,1.0mL/min,λ＝254nm,t(minor)＝7.49min,t(major)＝9.17min.
43.1mg,47％yield,96％ee.分析数据:[α]D 26＝-231.2(c＝0.1丙酮).1H NMR(400MHz,CD2Cl2)δ8.57(d,J＝5.2Hz,1H),7.80(d,J＝1.6Hz,1H),7.72(dt,J＝6.8,1.2Hz,2H),7.56-7.51(m,2H),7.50-7.47(m,1H),7.35(dd,J＝5.2,2.0Hz,1H),4.76(dd,J＝2.8,1.6Hz,1H),4.32(t,J＝2.0Hz,1H),4.26(t,J＝2.4Hz,1H),4.05(s,5H),2.40(s,3H).13CNMR(101MHz,CD2Cl2)δ161.5,150.1,148.7,139.6,129.9,129.7,127.8,120.8,119.3,84.43,84.40,73.0,71.1,69.9,67.9,16.1.IR(薄膜):νmax(cm-1)＝2952,2918,2860,1591,1539,1485,1447,1410,1374,1263,1208,1103,1075,1049,1032,999,885,835,812,786,759,734,694,655,614.HRMS(ESI)计算值C22H20[56Fe]N[M+H]+:354.0940.实测值:354.0935.手性柱Daicel Chiralpak IG(4.6×250mm),正己烷/异丙醇＝95/05,1.0mL/min,λ＝254nm,t(major)＝6.86min,t(minor)＝7.73min.eeSM＝99.48％；eePR＝95.52％；Calculated conversion,C＝eeSM/(eeSM+eePR)＝51％；Selectivity(s)＝ln[(1-C)(1-eeSM)]/ln[(1-C)(1+eeSM)]＝258.
实施例43
卤代芳烃III为对甲氧基溴苯，35.5mg,43％yield,95％ee.分析数据:[α]D 27＝+49.6(c＝0.1丙酮).1H NMR(400MHz,CD2Cl2)δ8.38(d,J＝5.6Hz,1H),7.19-7.16(m,2H),7.01(d,J＝2.4Hz,1H),6.74-6.71(m,3H),4.43(d,J＝2.4Hz,1H),4.34(d,J＝2.4Hz,1H),4.08(s,5H),3.77(s,3H),3.73(s,3H),2.11(s,3H).13C NMR(101MHz,CD2Cl2)δ165.7,160.3,158.9,150.6,131.2,113.8,113.5,108.3,88.4,86.9,85.6,72.3,70.0,68.4,56.0,55.7,14.9.IR(薄膜):νmax(cm-1)＝2953,2916,2834,1600,1554,1518,1482,1454,1433,1374,1301,1278,1242,1175,1104,1080,1031,1000,816,792,733.HRMS(ESI)计算值C24H24[56Fe]NO2[M+H]+:414.1151.实测值:414.1145.手性柱Daicel Chiralcel OD-H(4.6×250mm),正己烷/异丙醇＝90/10,1.0mL/min,λ＝254nm,t(minor)＝7.78min,t(major)＝10.37min.
28.7mg,47％yield,89％ee.分析数据:[α]D 24＝-145.6(c＝0.1丙酮).1H NMR(400MHz,CD2Cl2)δ8.35(d,J＝5.6Hz,1H),7.10(d,J＝2.8Hz,1H),6.69(dd,J＝5.6,2.4Hz,1H),4.67(dd,J＝2.8,1.6Hz,1H),4.29-4.27(m,1H),4.21(t,J＝2.4Hz,1H),4.03(s,5H),3.88(s,3H),2.34(s,3H).13C NMR(101MHz,CD2Cl2)δ166.3,162.3,150.9,108.8,107.5,84.4,84.3,72.8,71.0,69.8,67.7,55.8,16.1.IR(薄膜):νmax(cm-1)＝3087,3005,2916,2837,1588,1562,1488,1473,1457,1429,1392,1376,1296,1256,1231,1200,1180,1152,1103,1036,1001,959,808,749,735,710,655.HRMS(ESI)计算值C17H18[56Fe]NO[M+H]+:308.0732.实测值:308.0724.手性柱Daicel Chiralpak IG(4.6×250mm),正己烷/异丙醇＝95/05,1.0mL/min,λ＝254nm,t(major)＝8.84min,t(minor)＝9.97min.eeSM＝88.74％；eePR＝95.14％；Calculated conversion,C＝eeSM/(eeSM+eePR)＝48％；Selectivity(s)＝ln[(1-C)(1-eeSM)]/ln[(1-C)(1+eeSM)]＝120.
实施例44
卤代芳烃III为对甲氧基溴苯，39.7mg,45％yield,96％ee.分析数据:[α]D 24＝-5.6(c＝0.1丙酮).1H NMR(400MHz,CD2Cl2)δ8.52(d,J＝4.8Hz,1H),7.53-7.48(m,1H),7.37-7.33(m,3H),7.13(dd,J＝7.2,4.8Hz,1H),6.82(d,J＝8.0Hz,2H),4.85(s,1H),4.48(s,1H),4.06(s,5H),3.82(s,3H),0.32(s,9H).13C NMR(101MHz,CD2Cl2)δ159.4,159.2,149.3,136.1,131.6,130.8,125.3,121.7,114.0,91.4,86.9,77.4,75.7,73.4,72.1,56.0,0.2.IR(薄膜):νmax(cm-1)＝2952,2899,2833,1609,1586,1562,1519,1483,1442,1406,1372,1293,1242,1174,1148,1125,1105,1054,1038,1001,943,923,830,813,785,747,692,634.HRMS(ESI)计算值C25H28[56Fe]NOSi[M+H]+:442.1284.实测值:442.1281.手性柱Daicel Phenomenex Lux 5u Cellulose-2(4.6×250mm),正己烷/异丙醇＝95/05,1.0mL/min,λ＝254nm,t(minor)＝5.28min,t(major)＝6.37min.
27.5mg,41％yield,94％ee.分析数据:[α]D 27＝-60.8(c＝0.1丙酮).1H NMR(400MHz,CD2Cl2)δ8.48(dd,J＝4.0,1.2Hz,1H),7.61(td,J＝7.6,2.0Hz,1H),7.46(d,J＝8.0Hz,1H),7.09(ddd,J＝7.2,4.8,1.2Hz,1H),5.06(dd,J＝2.8,1.6Hz,1H),4.89(d,J＝1.6Hz,1H),4.36-4.34(m,1H),4.01(s,5H),0.29(s,9H).13C NMR(101MHz,CD2Cl2)δ159.8,150.0,136.7,121.3,120.9,87.4,75.5,73.0,70.8,70.6,0.2.IR(薄膜):νmax(cm-1)＝2954,1601,1556,1494,1441,1408,1382,1307,1244,1203,1136,1104,1051,999,909,863,830,809,750,690,633.HRMS(ESI)计算值C18H22[56Fe]NSi[M+H]+:336.0865.实测值:336.0864.手性柱Daicel Chiralcel OJ-3(SFC:3.0mm,I.D.:150mm),CO2/MeOH＝90/10,1.0mL/min,λ＝214nm,t(major)＝5.75min,t(minor)＝6.30min.eeSM＝94.48％；eePR＝95.78％；Calculated conversion,C＝eeSM/(eeSM+eePR)＝50％；Selectivity(s)＝ln[(1-C)(1-eeSM)]/ln[(1-C)(1+eeSM)]＝169.
实施例44
卤代芳烃III为对甲氧基溴苯，43.5mg,45％yield,95％ee.分析数据:[α]D 28＝+11.7(c＝0.1丙酮).1H NMR(400MHz,CD2Cl2)δ8.48(ddd,J＝4.8,2.0,0.8Hz,1H),7.49(td,J＝8.0,2.0Hz,1H),7.40-7.33(m,3H),7.10(ddd,J＝7.6,5.2,1.2Hz,1H),6.82(d,J＝8.8Hz,2H),4.80(d,J＝1.6Hz,1H),4.45(d,J＝1.6Hz,1H),4.04(s,5H),3.82(s,3H),1.10(t,J＝8.0Hz,9H),0.84(q,J＝8.0Hz,7H).13C NMR(101MHz,CD2Cl2δ159.6,159.2,149.6,135.8,131.6,131.0,125.0,121.5,114.0,91.0,86.9,77.9,76.1,72.2,71.0,56.0,8.4,5.4.IR(薄膜):νmax(cm-1)＝2952,1600,1519,1482,1458,1411,1385,1294,1243,1206,1175,1125,1104,1052,1033,1001,924,814,752,734,695.HRMS(ESI)计算值C28H34[56Fe]NOSi[M+H]+:484.1754.实测值:484.1753.手性柱Daicel Phenomenex Lux 5u Cellulose-2(4.6×250mm),正己烷/异丙醇＝95/05,1.0mL/min,λ＝254nm,t(major)＝5.09min,t(minor)＝6.00min.
39.3mg,46％yield,98％ee.分析数据:[α]D 27＝-138.3(c＝0.1丙酮).1H NMR(400MHz,CD2Cl2)δ8.48(d,J＝5.2Hz,1H),7.60(td,J＝7.6,1.6Hz,1H),7.46(d,J＝8.0Hz,1H),7.08(dd,J＝7.2,4.8Hz,1H),5.06(d,J＝1.6Hz,1H),4.86(s,1H),4.36-4.28(m,1H),4.00(s,5H),1.07(t,J＝8.0Hz,9H),0.81(q,J＝7.6Hz,6H).13C NMR(101MHz,CD2Cl2)δ159.9,150.0,136.6,121.3,120.9,87.2,76.0,73.4,73.1,70.63,70.55,8.4,5.3.IR(薄膜):νmax(cm-1)＝2952,2900,1601,1585,1562,1519,1488,1450,1430,1415,1377,1244,1162,1067,1034,899,827,786,748,691.HRMS(ESI)计算值C21H28[56Fe]NSi[M+H]+:378.1335.实测值:378.1340.手性柱Daicel Chiralcel OJ-3(SFC:3.0mm,I.D.:150mm),CO2/MeOH＝95/05,1.0mL/min,λ＝230nm,t(major)＝8.85min,t(minor)＝16.81min.eeSM＝98.00％；eePR＝95.14％；Calculated conversion,C＝eeSM/(eeSM+eePR)＝51％；Selectivity(s)＝ln[(1-C)(1-eeSM)]/ln[(1-C)(1+eeSM)]＝185.
实施例46
卤代芳烃III为对甲氧基溴苯，42.6mg,45％yield,90％ee.分析数据:m.p.:119.2-120.9℃.[α]D 24＝+40.7(c＝0.1丙酮).1H NMR(400MHz,CD2Cl2)δ8.51(ddd,J＝4.8,2.0,1.2Hz,1H),7.55(d,J＝8.8Hz,2H),7.48(td,J＝8.0,2.0Hz,1H),7.42(d,J＝8.8Hz,2H),7.34(dt,J＝8.4,0.8Hz,1H),7.11(ddd,J＝7.6,4.8,1.2Hz,1H),6.90(d,J＝8.8Hz,2H),6.84(d,J＝8.8Hz,2H),5.36(d,J＝1.6Hz,1H),4.99(d,J＝1.6Hz,1H),3.94(s,5H),3.83(s,6H).13C NMR(101MHz,CD2Cl2)δ159.4,159.3,159.2,149.6,135.8,131.8,131.0,130.7,128.0,125.0,121.6,114.7,114.0,89.1,86.3,84.9,73.3,70.5,68.3,56.0.IR(薄膜):νmax(cm-1)＝2993,2932,2832,1585,1564,1520,1492,1455,1424,1330,1285,1244,1201,1150,1104,1059,999,925,818,784,738,689.HRMS(ESI)计算值C29H26[56Fe]NO2[M+H]+:476.1308.实测值:476.1310.手性柱Daicel Phenomenex Lux 5u Cellulose-2(4.6×250mm),正己烷/异丙醇＝80/20,0.7mL/min,λ＝254nm,t(minor)＝13.71min,t(major)＝15.26min.
32.7mg,44％yield,96％ee.分析数据:[α]D 27＝-57.5(c＝0.1丙酮).1H NMR(400MHz,CD2Cl2)δ8.49(ddd,J＝4.8,2.0,0.8Hz,1H),7.62(td,J＝8.0,2.0Hz,1H),7.54-7.47(m,3H),7.10(ddd,J＝7.2,4.8,1.2Hz,1H),6.89(d,J＝8.8Hz,2H),5.40(t,J＝1.6Hz,1H),5.04(dd,J＝2.8,1.6Hz,1H),4.84(dd,J＝2.8,1.6Hz,1H),3.91(s,5H),3.83(s,3H).13C NMR(101MHz,CD2Cl2)δ159.8,159.2,150.0,136.7,131.4,128.0,121.3,120.7,114.7,88.4,85.0,71.8,68.6,68.4,66.0,56.0.IR(薄膜):νmax(cm-1)＝2970,2918,1609,1584,1562,1524,1498,1454,1439,1417,1288,1264,1243,1176,1147,1104,1045,1027,1000,894,827,809,784,742,700,648.HRMS(ESI)计算值C22H20[56Fe]NO[M+H]+:370.0889.实测值:370.0888.手性柱Daicel Phenomenex Lux 5u Cellulose-2(4.6×250mm),正己烷/异丙醇＝70/30,0.7mL/min,λ＝254nm,t(major)＝9.47min,t(minor)＝12.18min.eeSM＝95.88％；eePR＝90.38％；Calculated conversion,C＝eeSM/(eeSM+eePR)＝51％；Selectivity(s)＝ln[(1-C)(1-eeSM)]/ln[(1-C)(1+eeSM)]＝77.
实施例47
卤代芳烃III为对甲氧基溴苯，45.6mg,45％yield,76％ee.分析数据:[α]D 23＝+4.2(c＝0.1丙酮).1H NMR(400MHz,CD2Cl2)δ8.52(ddd,J＝4.8,1.6,0.8Hz,1H),7.49(td,J＝7.6,1.6Hz,1H),7.43(d,J＝8.8Hz,2H),7.35-7.32(m,1H),7.12(ddd,J＝7.6,4.8,1.2Hz,1H),6.85(d,J＝8.8Hz,2H),6.79(d,J＝2.0Hz,2H),6.38(t,J＝2.4Hz,1H),5.43(d,J＝1.6Hz,1H),5.04(d,J＝1.6Hz,1H),3.98(s,5H),3.85(s,6H),3.83(s,3H).13C NMR(101MHz,CD2Cl2)δ161.7,159.4,159.1,149.7,141.4,135.8,131.8,130.5,125.0,121.7,114.1,105.0,99.2,89.5,85.7,85.3,73.5,71.1,68.9,56.1,56.0.IR(薄膜):νmax(cm-1)＝2993,2932,2832,1585,1564,1520,1492,1455,1424,1330,1285,1244,1201,1150,1104,1058,1000,925,903,818,785,738,689.HRMS(ESI)计算值C30H28[56Fe]NO3[M+H]+:506.1413.实测值:506.1415.手性柱Daicel Phenomenex Lux 5u Cellulose-4(4.6×250mm),正己烷/异丙醇＝90/10,0.7mL/min,λ＝214nm,t(major)＝21.95min,t(minor)＝24.66min.
35.3mg,44％yield,95％ee.分析数据:[α]D 24＝-45.0(c＝0.1丙酮).1H NMR(400MHz,CD2Cl2)δ8.41-8.31(m,1H),7.50(td,J＝7.6,1.6Hz,1H),7.37(dt,J＝8.0,1.2Hz,1H),6.98(ddd,J＝7.2,4.8,1.2Hz,1H),6.62(d,J＝2.4Hz,2H),6.23(t,J＝2.4Hz,1H),5.22-5.16(m,1H),4.94(dd,J＝2.4,1.2Hz,1H),4.76(dd,J＝2.8,1.6Hz,1H),3.81(s,5H),3.72(s,6H).13C NMR(101MHz,CD2Cl2)δ161.7,159.5,150.0,141.7,136.8,121.5,120.8,105.1,99.1,87.8,85.3,72.0,69.2,68.8,66.6,56.1.IR(薄膜):νmax(cm-1)＝2968,2919,2848,1609,1584,1562,1524,1498,1455,1439,1418,1288,1264,1243,1176,1147,1104,1044,1027,1000,894,827,809,784,742,700,648.HRMS(ESI)计算值C23H22[56Fe]NO2[M+H]+:400.0995.实测值:400.0991.手性柱Daicel Phenomenex Lux 5u Cellulose-2(4.6×250mm),正己烷/异丙醇＝80/20,0.7mL/min,λ＝286nm,t(major)＝13.06min,t(minor)＝17.47min.eeSM＝95.34％；eePR＝75.68％；Calculated conversion,C＝eeSM/(eeSM+eePR)＝56％；Selectivity(s)＝ln[(1-C)(1-eeSM)]/ln[(1-C)(1+eeSM)]＝27.
实施例48
卤代芳烃III为对甲氧基溴苯，41.9mg,46％yield,86％ee.分析数据:[α]D 23＝+48.1(c＝0.1丙酮).1H NMR(400MHz,CD2Cl2)δ8.34(d,J＝4.8Hz,1H),7.36(d,J＝8.8Hz,2H),7.20(d,J＝1.6Hz,1H),6.95(dd,J＝4.8,1.6Hz,1H),6.81(d,J＝8.8Hz,2H),4.78(d,J＝1.6Hz,1H),4.47(d,J＝1.6Hz,1H),4.05(s,5H),3.82(s,3H),2.25(s,3H),0.31(s,9H).13C NMR(101MHz,CD2Cl2)δ159.2,159.1,149.3,146.9,131.5,131.0,125.7,122.7,113.9,91.0,87.5,77.0,75.9,73.1,72.0,56.0,21.5,0.2.IR(薄膜):νmax(cm-1)＝2951,1599,1519,1482,1458,1411,1385,1366,1294,1242,1206,1175,1125,1104,1052,1033,1001,924,813,752,733,694,634.HRMS(ESI)计算值C26H30[56Fe]NOSi[M+H]+:456.1441.实测值:456.1441.手性柱Daicel Chiralcel OD-H(4.6×250mm),正己烷/异丙醇＝95/05,1.0mL/min,λ＝254nm,t(major)＝4.66min,t(minor)＝5.55min.
30.0mg,43％yield,>99％ee.分析数据:[α]D 27＝-48.1(c＝0.1丙酮).1H NMR(400MHz,CD2Cl2)δ8.33(d,J＝4.8Hz,1H),7.29(d,J＝1.6Hz,1H),6.93(dd,J＝5.2,1.6Hz,1H),5.05(dd,J＝2.8,1.6Hz,1H),4.87(t,J＝1.2Hz,1H),4.33(dd,J＝2.4,1.2Hz,1H),4.01(s,5H),2.36(s,3H),0.29(s,9H).13C NMR(101MHz,CD2Cl2)δ159.5,149.7,147.8,122.5,121.6,87.6,75.31,75.25,73.0,70.8,70.5,21.6,0.2.IR(薄膜):νmax(cm-1)＝2954,1600,1556,1519,1494,1442,1408,1382,1307,1244,1203,1172,1136,1104,1051,999,909,863,830,809,750,690,633.HRMS(ESI)计算值C19H23[56Fe]NSi[M+H]+:350.1022.实测值:350.1027.手性柱Daicel Chiralcel OD-3(SFC:3.0mm,I.D.:150mm),CO2/MeOH＝70/30,1.0mL/min,λ＝214nm,t(major)＝1.27min,t(minor)＝2.13min.eeSM＝99.48％；eePR＝85.84％；Calculated conversion,C＝eeSM/(eeSM+eePR)＝54％；Selectivity(s)＝ln[(1-C)(1-eeSM)]/ln[(1-C)(1+eeSM)]＝76.
实施例49
卤代芳烃III为对甲氧基溴苯，41.7mg,46％yield,88％ee.分析数据:[α]D 26＝+7.5(c＝0.1丙酮).1H NMR(400MHz,CD2Cl2)δ8.32(d,J＝2.4Hz,1H),7.36-7.33(m,2H),7.31(dd,J＝8.0,2.0Hz,1H),7.24(d,J＝8.0Hz,1H),6.83-6.79(m,2H),4.79(d,J＝1.6Hz,1H),4.44(d,J＝1.6Hz,1H),4.04(s,5H),3.82(s,3H),2.30(s,3H),0.31(s,9H).13C NMR(101MHz,CD2Cl2)δ159.1,156.3,149.9,136.5,131.5,131.1,131.0,124.5,113.9,91.1,87.5,77.1,75.5,73.0,72.0,56.0,18.7,0.2.IR(薄膜):νmax(cm-1)＝2951,2834,1599,1553,1519,1482,1458,1411,1385,1366,1294,1242,1206,1175,1143,1125,1104,1052,1033,1001,957,924,813,752,733,694,634.HRMS(ESI)计算值C26H30[56Fe]NOSi[M+H]+:456.1441.实测值:456.1434.手性柱Daicel Chiralcel OD-H(4.6×250mm),正己烷/异丙醇＝90/10,1.0mL/min,λ＝254nm,t(minor)＝4.77min,t(major)＝7.12min.
30.7mg,44％yield,99％ee.分析数据:[α]D 25＝-80.1(c＝0.1丙酮).1H NMR(400MHz,CD2Cl2)δ8.31(d,J＝2.4Hz,1H),7.43(dd,J＝8.0,2.4Hz,1H),7.36(d,J＝8.0Hz,1H),5.02(dd,J＝2.0,1.2Hz,1H),4.84(t,J＝1.2Hz,1H),4.31(dd,J＝2.4,1.6Hz,1H),3.99(s,5H),2.29(s,3H),0.28(s,9H).13C NMR(101MHz,CD2Cl2)δ156.7,150.4,137.4,130.8,120.4,87.8,75.2,75.1,72.7,70.6,70.5,18.7,0.2.IR(薄膜):νmax(cm-1)＝2954,1600,1556,1519,1494,1441,1408,1382,1307,1244,1203,1172,1136,1104,1051,999,928,909,863,830,809,750,690,660,633.HRMS(ESI)计算值C19H24[56Fe]NSi[M+H]+:350.1022.实测值:350.1024.手性柱Daicel Chiralcel OD-3(SFC:3.0mm,I.D.:150mm),CO2/MeOH＝90/10,1.0mL/min,λ＝214nm,t(major)＝2.63min,t(minor)＝2.95min.eeSM＝99.30％；eePR＝87.90％；Calculated conversion,C＝eeSM/(eeSM+eePR)＝53％；Selectivity(s)＝ln[(1-C)(1-eeSM)]/ln[(1-C)(1+eeSM)]＝86.
实施例50
卤代芳烃III为对甲氧基溴苯，41.3mg,45％yield,92％ee.分析数据:[α]D 25＝+2.2(c＝0.1丙酮).1H NMR(400MHz,CD2Cl2)δ8.44(dd,J＝8.8,5.6Hz,1H),7.37(d,J＝8.8Hz,2H),7.05(dd,J＝10.8,2.8Hz,1H),6.92-6.77(m,3H),4.85(d,J＝1.6Hz,1H),4.48(d,J＝1.6Hz,1H),4.06(s,5H),3.83(s,3H),0.31(s,9H).13C NMR(101MHz,CD2Cl2)δ168.9(J＝260.2Hz),163.2(J＝7.6Hz),159.4,151.9(J＝7.2Hz),131.6,130.4,114.1,111.7(J＝17.3Hz),109.5(J＝16.8Hz),91.7,85.8,77.8,75.7,73.7,72.1,56.0,0.2.19F NMR(377MHz,CD2Cl2)δ-105.6(m).IR(薄膜):νmax(cm-1)＝2952,2835,1601,1556,1519,1483,1457,1411,1385,1294,1243,1206,1176,1125,1105,1051,1034,1001,924,814,790,752,695,634.HRMS(ESI)计算值C25H27[56Fe]FNOSi[M+H]+:460.1190.实测值:460.1189.手性柱Daicel Chiralcel OD-3(SFC:3.0mm,I.D.:150mm),CO2/MeOH＝95/05,1.0mL/min,λ＝230nm,t(major)＝4.42min,t(minor)＝4.76min.
32.5mg,46％yield,85％ee.分析数据:[α]D 27＝-53.9(c＝0.1丙酮).1H NMR(400MHz,CD2Cl2)δ8.44(dd,J＝9.2,5.6Hz,1H),7.17(dd,J＝10.4,2.4Hz,1H),6.88-6.82(m,1H),5.05(dd,J＝2.8,1.2Hz,1H),4.87(t,J＝1.2Hz,1H),4.37(dd,J＝2.4,1.2Hz,1H),4.03(s,5H),0.29(s,9H).13C NMR(101MHz,CD2Cl2)δ169.7(J＝260.3Hz),163.6(J＝7.2Hz),152.4(J＝7.3Hz),109.2(J＝16.8Hz),107.9(J＝17.3Hz),86.2(J＝3.6Hz),76.1,75.8,73.2,71.0,70.7,0.15.19F NMR(377MHz,CD2Cl2)δ-105.3(m).IR(薄膜):νmax(cm-1)＝3079,2968,2947,2916,1584,1562,1488,1449,1415,1376,1290,1265,1226,1150,1087,1068,1036,1003,984,921,807,784,739,709,645,619.HRMS(ESI)计算值C18H21[56Fe]NFSi[M+H]+:354.0771.实测值:354.0780.手性柱Daicel Chiralpak IC-3(SFC:3.0mm,I.D.:150mm),CO2/MeOH＝90/10,1.0mL/min,λ＝230nm,t(major)＝1.83min,t(minor)＝2.42min.eeSM＝85.22％；eePR＝91.72％；Calculated conversion,C＝eeSM/(eeSM+eePR)＝48％；Selectivity(s)＝ln[(1-C)(1-eeSM)]/ln[(1-C)(1+eeSM)]＝63.
实施例51
卤代芳烃III为对甲氧基溴苯，55.1mg,56％yield,56％ee.分析数据:[α]D 25＝+41.2(c＝0.1丙酮).1H NMR(400MHz,CD2Cl2)δ8.60(d,J＝5.6Hz,1H),7.86(dd,J＝8.4,1.2Hz,1H),7.83-7.77(m,1H),7.62(d,J＝5.6Hz,1H),7.59-7.32(m,1H),7.35-7.28(m,1H),7.15(d,J＝8.8Hz,2H),6.60(d,J＝8.8Hz,2H),4.65(d,J＝1.6Hz,1H),4.55(d,J＝1.6Hz,1H),4.27(s,5H),3.69(s,3H),0.36(s,9H).13C NMR(101MHz,CD2Cl2)δ159.7,158.7,143.0,136.6,131.6,130.3,130.2,129.3,128.6,127.4,127.2,120.2,113.9,91.4,90.5,78.5,73.5,72.3,55.8,0.4.IR(薄膜):νmax(cm-1)＝3063,2997,2952,2900,2833,1584,1482,1461,1409,1373,1314,1287,1245,1202,1178,1155,1122,1107,1080,1049,1000,964,924,836,815,785,748,698,629.HRMS(ESI)计算值C29H30[56Fe]NOSi[M+H]+:492.1441.实测值:492.1445.手性柱Daicel Chiralpak AD-3(4.6×250mm),正己烷/异丙醇＝95/05,0.7mL/min,λ＝214nm,t(major)＝5.11min,t(minor)＝9.00min.
30.8mg,40％yield,99％ee.分析数据:[α]D 24＝-52.3(c＝0.1丙酮).1H NMR(400MHz,CD2Cl2)δ8.95-8.88(m,1H),8.43(d,J＝5.6Hz,1H),7.88-7.84(m,1H),7.72-7.63(m,2H),7.54(d,J＝5.6Hz,1H),5.16(dd,J＝2.4,1.2Hz,1H),4.95(d,J＝1.2Hz,1H),4.45(dd,J＝2.4,1.6Hz,1H),4.14(s,5H),0.33(s,9H).13C NMR(101MHz,CD2Cl2)δ159.8,142.8,137.6,130.3,128.0,127.9,127.5,127.3,119.5,88.6,76.5,75.1,75.0,74.2,70.7,0.3.IR(薄膜):νmax(cm-1)＝2969,2947,2916,1584,1562,1488,1449,1415,1376,1150,1068,1037,1003,808,785,740.HRMS(ESI)计算值C22H24[56Fe]NSi[M+H]+:386.1022.实测值:386.1021.手性柱Daicel Chiralcel OD-3(SFC:3.0mm,I.D.:150mm),CO2/MeOH＝95/05,1.0mL/min,λ＝214nm,t(minor)＝9.14min,t(major)＝10.43min.eeSM＝99.46％；eePR＝56.26％；Calculated conversion,C＝eeSM/(eeSM+eePR)＝64％；Selectivity(s)＝ln[(1-C)(1-eeSM)]/ln[(1-C)(1+eeSM)]＝19.
实施例52
卤代芳烃III为对甲硫基溴苯，41.2mg,45％yield,92％ee.分析数据:[α]D 27＝+13.7(c＝0.1丙酮).1H NMR(400MHz,CD2Cl2)δ8.51-8.48(m,1H),7.52(td,J＝7.6,2.0Hz,1H),7.38-7.34(m,3H),7.18-7.10(m,3H),4.84(d,J＝1.6Hz,1H),4.51(d,J＝1.6Hz,1H),4.06(s,5H),2.51(s,3H),0.32(s,9H).13C NMR(101MHz,CD2Cl2)δ159.3,149.6,137.2,136.0,135.9,130.9,126.5,125.1,121.7,90.6,87.3,77.5,76.0,73.7,72.2,16.3,0.2.IR(薄膜):νmax(cm-1)＝2952,2899,2833,1609,1586,1562,1519,1483,1442,1406,1372,1293,1242,1174,1148,1125,1105,1054,1030,1001,943,923,830,813,785,747,691,634.HRMS(ESI)计算值C25H28[56Fe]NSSi[M+H]+:458.1056.实测值:458.1050.手性柱DaicelPhenomenex Lux 5u Cellulose-2(4.6×250mm),正己烷/异丙醇＝95/05,1.0mL/min,λ＝254nm,t(major)＝4.94min,t(minor)＝5.87min.
II-28.深红色液体,28.8mg,43％yield,95％ee.eeSM＝95.14％；eePR＝92.06％；Calculated conversion,C＝eeSM/(eeSM+eePR)＝51％；Selectivity(s)＝ln[(1-C)(1-eeSM)]/ln[(1-C)(1+eeSM)]＝91.
实施例53
卤代芳烃III为4-N,N-二甲基胺溴苯，42.7mg,47％yield,93％ee.分析数据:[α]D 25＝+3.6(c＝0.1丙酮).1H NMR(400MHz,CD2Cl2)δ8.49(ddd,J＝5.2,2.0,1.2Hz,1H),7.49(td,J＝7.6,1.6Hz,1H),7.39(dt,J＝8.0,0.8Hz,1H),7.31-7.26(m,2H),7.10(ddd,J＝7.6,4.8,1.2Hz,1H),6.67-6.64(m,2H),4.81(d,J＝1.6Hz,1H),4.44(d,J＝1.6Hz,1H),4.04(s,5H),2.96(s,6H),0.31(s,9H).13C NMR(101MHz,CD2Cl2)δ159.8,150.2,149.5,135.7,131.2,126.1,125.1,121.4,112.6,92.1,87.0,77.0,75.4,72.9,72.0,41.2,0.2.IR(薄膜):νmax(cm-1)＝2951,2900,2833,1609,1586,1562,1519,1483,1442,1407,1373,1294,1242,1174,1148,1125,1105,1054,1030,1002,924,831,813,785,747,691,634.HRMS(ESI)计算值C26H31[56Fe]N2Si[M+H]+:455.1600.实测值:455.1603.手性柱Daicel Chiralcel OD-H(4.6×250mm),正己烷/异丙醇＝95/05,1.0mL/min,λ＝254nm,t(minor)＝6.65min,t(major)＝10.08min.
II-28.深红色液体,28.9mg,43％yield,99％ee.eeSM＝98.50％；eePR＝93.10％；Calculated conversion,C＝eeSM/(eeSM+eePR)＝51％；Selectivity(s)＝ln[(1-C)(1-eeSM)]/ln[(1-C)(1+eeSM)]＝136.
实施例54
卤代芳烃III为对氟溴苯，41.1mg,48％yield,91％ee.分析数据:[α]D 24＝-26.0(c＝0.1丙酮).1H NMR(400MHz,CD2Cl2)δ8.48(ddd,J＝4.8,2.0,1.8Hz,1H),7.51(td,J＝7.6,2.0Hz,1H),7.46-7.39(m,2H),7.32(dt,J＝8.0,0.8Hz,1H),7.12(ddd,J＝7.6,4.8,1.2Hz,1H),7.03-6.93(m,2H),4.84(d,J＝1.6Hz,1H),4.49(d,J＝1.6Hz,1H),4.06(s,5H),0.32(s,9H).13C NMR(101MHz,CD2Cl2)δ163.4(J＝245.4Hz),159.2,149.7,135.95,135.1(J＝3.3Hz),132.1(J＝7.9Hz),125.0,121.7,115.3(J＝21.3Hz),90.3,87.5,77.6,75.9,73.7,72.2,0.2.19F NMR(377MHz,CD2Cl2)δ-117.1(m).IR(薄膜):νmax(cm-1)＝2952,2899,1583,1482,1460,1408,1373,1287,1244,1202,1177,1154,1121,1107,1080,1048,999,924,835,814,784,747,698,629.HRMS(ESI)计算值C24H25[56Fe]FNSi[M+H]+:430.1084.实测值:430.1088.手性柱Daicel Chiralcel OD-H(4.6×250mm),正己烷/异丙醇＝95/05,0.7mL/min,λ＝254nm,t(major)＝7.92min,t(minor)＝9.47min.
II-28.深红色液体,32.5mg,44％yield,>99％ee.eeSM＝99.92％；eePR＝90.50％；Calculated conversion,C＝eeSM/(eeSM+eePR)＝52％；Selectivity(s)＝ln[(1-C)(1-eeSM)]/ln[(1-C)(1+eeSM)]＝154.
实施例55
卤代芳烃III为对乙酰基溴苯，40.8mg,45％yield,77％ee.分析数据:[α]D 27＝-6.6(c＝0.1丙酮).1H NMR(400MHz,CD2Cl2)δ8.48(ddd,J＝5.2,2.0,1.2Hz,1H),7.85-7.82(m,2H),7.54-7.50(m,3H),7.37(dd,J＝8.0,1.2Hz,1H),7.14(ddd,J＝7.6,5.2,1.2Hz,1H),4.87(d,J＝1.6Hz,1H),4.60(d,J＝1.6Hz,1H),4.08(s,5H),2.59(s,3H),0.33(s,9H).13C NMR(101MHz,CD2Cl2)δ198.2,159.0,149.7,145.3,136.1,135.9,130.5,128.5,125.1,121.8,89.2,88.0,77.8,76.9,74.5,72.4,27.2,0.2.IR(薄膜):νmax(cm-1)＝2954,2899,1677,1601,1586,1561,1483,1441,1402,1355,1266,1246,1181,1125,1107,1073,1053,1002,955,943,924,833,815,786,735,700,612.HRMS(ESI)计算值C26H28[56Fe]NOSi[M+H]+:454.1284.实测值:454.1286.手性柱Daicel Chiralpak AD-H(4.6×250mm),正己烷/异丙醇＝95/05,1.0mL/min,λ＝254nm,t(major)＝5.77min,t(minor)＝7.78min.
II-28.深红色液体,29.4mg,44％yield,85％ee.eeSM＝85.00％；eePR＝76.88％；Calculated conversion,C＝eeSM/(eeSM+eePR)＝53％；Selectivity(s)＝ln[(1-C)(1-eeSM)]/ln[(1-C)(1+eeSM)]＝20.
实施例56
卤代芳烃III为46.4mg,48％yield,76％ee.分析数据:[α]D 27＝-3.4(c＝0.1丙酮).1H NMR(400MHz,CD2Cl2)δ8.50-8.47(m,1H),7.91(d,J＝8.4Hz,2H),7.55-7.48(m,3H),7.34(dt,J＝8.0,1.2Hz,1H),7.13(ddd,J＝7.6,4.8,1.2Hz,1H),4.88(d,J＝1.6Hz,1H),4.59(d,J＝1.6Hz,1H),4.36(q,J＝7.2Hz,2H),4.07(s,5H),1.39(t,J＝7.2Hz,3H),0.33(s,9H).13C NMR(101MHz,CD2Cl2)δ167.2,159.0,149.7,144.8,136.1,130.3,129.6,129.1,125.1,121.8,89.4,87.9,77.9,76.8,74.4,72.4,61.6,15.0,0.2.IR(薄膜):νmax(cm-1)＝2955,2900,1710,1606,1586,1563,1483,1443,1403,1367,1270,1246,1175,1125,1099,1053,1019,1002,924,835,815,786,774,746,705,630.HRMS(ESI)计算值C27H30[56Fe]NO2Si[M+H]+:484.1390.实测值:484.1394.手性柱Daicel Chiralpak IG(4.6×250mm),正己烷/异丙醇＝95/05,1.0mL/min,λ＝254nm,t(minor)＝7.74min,t(major)＝11.99min.
II-28.深红色液体,31.8mg,43％yield,85％ee.eeSM＝85.46％；eePR＝76.04％；Calculated conversion,C＝eeSM/(eeSM+eePR)＝53％；Selectivity(s)＝ln[(1-C)(1-eeSM)]/ln[(1-C)(1+eeSM)]＝20.
实施例57
卤代芳烃III为对氰基溴苯，40.0mg,46％yield,89％ee.分析数据:[α]D 27＝+2.1(c＝0.1丙酮).1H NMR(400MHz,CD2Cl2)δ8.47(ddd,J＝4.8,2.0,0.8Hz,1H),7.57(dd,J＝8.0,2.0Hz,1H),7.53(s,4H),7.37(dd,J＝8.0,1.2Hz,1H),7.15(ddd,J＝7.6,4.8,1.2Hz,1H),4.86(d,J＝1.6Hz,1H),4.59(d,J＝1.6Hz,1H),4.07(s,5H),0.32(s,9H).13C NMR(101MHz,CD2Cl2)δ158.7,149.8,145.5,136.2,132.2,130.9,124.9,122.0,120.0,110.2,88.4,88.1,77.7,77.2,74.9,72.5,0.2.IR(薄膜):νmax(cm-1)＝2953,2899,2223,1603,1586,1563,1513,1483,1444,1405,1374,1245,1207,1150,1123,1106,1086,1052,1039,1001,924,831,814,786,745,697,631.HRMS(ESI)计算值C25H25[56Fe]N2Si[M+H]+:437.1131.实测值:437.1139.HPLC:手性柱Daicel Chiralcel OD-H(4.6×250mm),正己烷/异丙醇＝95/05,1.0mL/min,λ＝254nm,t(major)＝6.01min,t(minor)＝7.98min.
II-28.深红色液体,29.5mg,44％yield,70％ee.eeSM＝70.30％；eePR＝88.86％；Calculated conversion,C＝eeSM/(eeSM+eePR)＝44％；Selectivity(s)＝ln[(1-C)(1-eeSM)]/ln[(1-C)(1+eeSM)]＝36.
实施例58
卤代芳烃III为3-甲氧基溴苯，37.9mg,43％yield,95％ee.分析数据:[α]D 25＝-7.3(c＝0.1丙酮).1H NMR(400MHz,CD2Cl2)δ8.49(ddd,J＝4.8,1.6,0.8Hz,1H),7.50(td,J＝7.6,2.0Hz,1H),7.36(dt,J＝8.0,1.2Hz,1H),7.21-7.16(m,1H),7.11(ddd,J＝7.6,4.8,1.2Hz,1H),7.03(dt,J＝7.6,1.2Hz,1H),6.98(dd,J＝2.4,1.6Hz,1H),6.79(ddd,J＝8.0,2.4,0.8Hz,1H),4.85(d,J＝1.6Hz,1H),4.53(d,J＝1.6Hz,1H),4.07(s,5H),3.73(s,3H),0.32(s,9H).13C NMR(101MHz,CD2Cl2)δ159.9,159.3,149.6,140.6,135.8,129.5,125.2,123.1,121.6,116.1,112.8,91.2,87.5,77.8,75.9,73.6,72.2,55.9,0.2.IR(薄膜):νmax(cm-1)＝2952,2900,2832,1583,1482,1460,1408,1373,1314,1287,1244,1202,1177,1154,1121,1107,1080,1047,999,924,835,813,784,746,697,628.HRMS(ESI)计算值C25H28[56Fe]NOSi[M+H]+:442.1284.实测值:442.1293.手性柱Daicel Chiralcel OD-H(4.6×250mm),正己烷/异丙醇＝95/05,1.0mL/min,λ＝254nm,t(major)＝4.63min,t(minor)＝6.93min.
II-28.深红色液体,30.8mg,46％yield,72％ee.eeSM＝71.98％；eePR＝94.88％；Calculated conversion,C＝eeSM/(eeSM+eePR)＝43％；Selectivity(s)＝ln[(1-C)(1-eeSM)]/ln[(1-C)(1+eeSM)]＝82.
实施例59
卤代芳烃III为38.4mg,42％yield,93％ee.分析数据:[α]D 25＝+24.0(c＝0.1丙酮).1H NMR(400MHz,CD2Cl2)δ8.48(ddd,J＝4.8,2.0,1.2Hz,1H),7.52(td,J＝7.6,2.0Hz,1H),7.38(dt,J＝8.0,1.2Hz,1H),7.11(ddd,J＝7.6,4.8,1.2Hz,1H),6.94(d,J＝1.6Hz,1H),6.90(dd,J＝8.0,2.0Hz,1H),6.72(d,J＝8.0Hz,1H),5.97(s,2H),4.82(d,J＝1.6Hz,1H),4.46(d,J＝1.6Hz,1H),4.06(s,5H),0.31(s,9H).13C NMR(101MHz,CD2Cl2)δ159.3,149.6,140.6,135.8,129.5,125.2,123.1,121.6,116.1,112.8,91.2,87.5,77.8,75.9,73.6,72.2,55.9,0.2.IR(薄膜):νmax(cm-1)＝2952,2891,2774,1585,1562,1505,1481,1454,1424,1409,1373,1332,1264,1228,1150,1109,1036,1001,925,833,809,785,744,694,622.HRMS(ESI)计算值C25H26[56Fe]NO2Si[M+H]+:456.1077.实测值:456.1076.手性柱Daicel Chiralcel OD-H(4.6×250mm),正己烷/异丙醇＝95/05,1.0mL/min,λ＝254nm,t(major)＝6.17min,t(minor)＝10.92min.
II-28.深红色液体,31.5mg,47％yield,90％ee.eeSM＝90.14％；eePR＝93.14％；Calculated conversion,C＝eeSM/(eeSM+eePR)＝49％；Selectivity(s)＝ln[(1-C)(1-eeSM)]/ln[(1-C)(1+eeSM)]＝87.
实施例60
卤代芳烃III为45.9mg,49％yield,84％ee.分析数据:[α]D 27＝+11.8(c＝0.1丙酮).1H NMR(400MHz,CD2Cl2)δ8.49(ddd,J＝4.8,1.6,0.8Hz,1H),7.51(td,J＝7.6,2.0Hz,1H),7.38(dt,J＝8.0,1.2Hz,1H),7.11(ddd,J＝7.2,4.8,1.2Hz,1H),6.96(d,J＝2.4Hz,1H),6.87(dd,J＝8.4,2.0Hz,1H),6.74(d,J＝8.4Hz,1H),4.81(d,J＝1.6Hz,1H),4.46(d,J＝1.6Hz,1H),4.27(s,4H),4.05(s,5H),0.31(s,9H).13C NMR(101MHz,CD2Cl2)δ159.4,149.6,143.7,143.2,135.8,132.1,125.1,123.7,121.6,119.1,117.2,91.1,87.3,77.5,75.7,73.3,72.1,65.3,65.3,0.2.IR(薄膜):νmax(cm-1)＝2952,2891,1586,1562,1505,1481,1454,1424,1409,1373,1264,1228,1150,1110,1036,1001,925,833,809,785,745,692,621.HRMS(ESI)计算值C26H28[56Fe]NO2Si[M+H]+:470.1233.实测值:470.1236.手性柱Daicel Chiralcel OD-H(4.6×250mm),正己烷/异丙醇＝95/05,1.0mL/min,λ＝254nm,t(major)＝8.72min,t(minor)＝13.45min.
II-28.深红色液体,31.8mg,43％yield,>99％ee.eeSM＝99.90％；eePR＝83.58％；Calculated conversion,C＝eeSM/(eeSM+eePR)＝54％；Selectivity(s)＝ln[(1-C)(1-eeSM)]/ln[(1-C)(1+eeSM)]＝82.
实施例61
卤代芳烃III为42.8mg,45％yield,92％ee.分析数据:[α]D 26＝+32.3(c＝0.1丙酮).1H NMR(400MHz,CD2Cl2)δ8.50-8.47(m,1H),7.96(d,J＝8.4Hz,1H),7.86-7.75(m,3H),7.48(td,J＝7.6,2.0Hz,1H),7.36(dd,J＝8.4,1.2Hz,1H),7.28(d,J＝8.4Hz,1H),7.12(ddd,J＝7.6,5.4,1.2Hz,1H),4.90(d,J＝1.6Hz,1H),4.65(d,J＝1.6Hz,1H),4.11(s,5H),2.71(s,3H),0.34(s,9H).13C NMR(101MHz,CD2Cl2)δ159.4,159.2,149.7,147.7,136.8,136.4,135.9,132.9,128.3,127.8,127.0,125.0,123.0,121.7,90.3,87.8,77.7,76.5,74.1,72.2,25.8,0.2.IR(薄膜):νmax(cm-1)＝2951,2918,1584,1562,1480,1440,1410,1368,1246,1222,1144,1110,1085,1054,1038,1000,924,860,835,813,784,742,697,661,628.HRMS(ESI)计算值C28H29[56Fe]N2Si[M+H]+:477.1444.实测值:477.1449.手性柱Daicel Phenomenex Lux 5u Cellulose-2(4.6×250mm),正己烷/异丙醇＝95/05,1.0mL/min,λ＝254nm,t(minor)＝10.70min,t(major)＝14.70min.
II-28.深红色液体,29.5mg,44％yield,62％ee.eeSM＝62.18％；eePR＝91.92％；Calculated conversion,C＝eeSM/(eeSM+eePR)＝40％；Selectivity(s)＝ln[(1-C)(1-eeSM)]/ln[(1-C)(1+eeSM)]＝45.
实施例62
(Sp)-II-1(28.0mg,0.1mmol)、IV(64.0mg,0.15mmol)、[Cp*RhCl2]2(1.6mg,0.0025mmol)和AgSbF6(7.2mg,0.02mmol)加入Schlenk反应管，随后向该管中加入甲醇(2.0mL)，然后将所得混合物在室温下搅拌。反应完成后(通过TLC监测)，反应混合物用乙酸乙酯(10.0mL)稀释并通过硅藻土过滤。减压除去溶剂，残余物通过硅胶柱层析(石油醚/乙酸乙酯＝50/1,v/v)纯化得到V。
38.0mg,83％yield,99％ee.[α]D 26＝-86.2(c＝0.1丙酮).1H NMR(400MHz,CD2Cl2)δ8.56(ddd,J＝4.8,1.6,0.8Hz,1H),8.15(td,J＝8.0,1.2Hz,1H),7.64(td,J＝7.6,2.0Hz,1H),7.16(ddd,J＝7.6,4.8,1.2Hz,1H),4.53(d,J＝2.4Hz,1H),4.33(d,J＝2.8Hz,1H),4.09(s,5H),2.24(s,3H),1.2-0.9(m,21H).13C NMR(101MHz,CD2Cl2)δ158.6,149.3,135.8,125.9,121.7,106.8,90.1,87.5,85.9,73.0,71.9,71.8,66.1,19.3,15.6,12.1.IR(薄膜):νmax(cm-1)＝2940,2921,2862,2143,1585,1564,1483,1460,1431,1379,1105,1056,999,984,881,815,787,758,742,729,672.HRMS(ESI)计算值C27H36[56Fe]NSi[M+H]+:458.1961.实测值:458.1968.手性柱Daicel Chiralcel OD-H(4.6×250mm),正己烷/异丙醇＝98/02,0.7mL/min,λ＝286nm,t(minor)＝4.97min,t(major)＝5.61min.
实施例63
在-78℃下，向(Sp)-II-1(1.0equiv)的乙醚溶液中加入叔丁基锂(1.5equiv)。将反应混合物在-78℃搅拌4小时。然后加入相应的亲电试剂(1.5equiv)。之后，将混合物升温至室温并搅拌过夜。将反应混合物用冰冷的水淬灭并用乙酸乙酯萃取。合并的有机层用盐水洗涤，用无水硫酸钠干燥并过滤。减压除去溶剂后，残余物经硅胶柱层析(石油醚/乙酸乙酯＝20/1,v/v)纯化得到VI。
25.1mg,71％yield,99％ee.[α]D 27＝-32.9(c＝0.1丙酮).1H NMR(400MHz,CD2Cl2)δ8.60(ddd,J＝5.2,2.0,1.2Hz,1H),7.90(dt,J＝8.0,0.8Hz,1H),7.73(td,J＝7.6,1.6Hz,1H),7.22(ddd,J＝7.6,4.8,1.2Hz,1H),4.49(d,J＝2.8Hz,1H),4.27(d,J＝2.4Hz,1H),4.17(s,5H),2.09(s,3H).13C NMR(101MHz,CD2Cl2)δ157.2,149.6,135.9,126.8,122.2,86.3,83.7,80.6,73.6,69.8,69.4,15.2.IR(薄膜):νmax(cm-1)＝2951,2906,2871,1609,1585,1563,1519,1481,1455,1429,1410,1375,1295,1281,1260,1242,1175,1146,1105,1075,1053,1034,1003,896,816,786,744,725,694,675.HRMS(ESI)计算值C16H15[56Fe]NBr[M+H]+:355.9732.实测值:355.9737.手性柱Daicel Chiralcel OJ-H(4.6×250mm),正己烷/异丙醇＝95/05,0.7mL/min,λ＝254nm,t(minor)＝8.82min,t(major)＝10.64min.
33.8mg,70％yield,99％ee.[α]D 27＝-415.5(c＝0.1丙酮).1H NMR(400MHz,CD2Cl2)δ8.63-8.53(m,1H),7.94-7.83(m,2H),7.75-7.64(m,2H),7.39-7.31(m,1H),7.31-7.23(m,2H),7.19-7.12(m,1H),4.33(d,J＝2.4Hz,1H),3.97(s,1H),3.96(s,5H),2.31(s,3H).13C NMR(101MHz,CD2Cl2)δ160.1,148.5,140.2,136.6,129.7,128.4,123.1,121.2,119.9,85.1,84.5,74.5,73.1,73.0,58.7,16.6.IR(薄膜):νmax(cm-1)＝2984,2912,1587,1564,1479,1445,1428,1406,1372,1270,1245,1101,1062,1016,993,806,783,744,731,693,676,646,623.HRMS(ESI)计算值C22H19[56Fe]NTe[M+H]+:482.9924.实测值:482.9937.手性柱Daicel Chiralcel OD-H(4.6×250mm),正己烷/异丙醇＝95/05,1.0mL/min,λ＝254nm,t(major)＝5.85min,t(minor)＝7.82min.
32.0mg,81％yield,99％ee.[α]D 27＝-17.6(c＝0.1丙酮).1H NMR(400MHz,CD2Cl2)δ8.50(d,J＝4.0Hz,1H),7.75-7.61(m,2H),7.17-7.12(m,1H),4.38(d,J＝2.4Hz,1H),4.15(d,J＝2.4Hz,1H),4.07(s,5H),2.15(s,3H),0.26(s,9H).13C NMR(101MHz,CD2Cl2)δ160.0,149.2,135.9,125.4,121.5,92.2,87.0,75.8,73.3,72.9,71.0,14.6,0.8.IR(薄膜):νmax(cm-1)＝2969,2904,1585,1563,1480,1447,1432,1407,1377,1229,1143,1104,1053,1000,811,787,745,662.HRMS(ESI)计算值C19H24[56Fe]NGe[M+H]+:396.0465.实测值:396.0462.手性柱Daicel Chiralcel OD-H(4.6×250mm),正己烷/异丙醇＝98/02,0.7mL/min,λ＝230nm,t(major)＝5.73min,t(minor)＝6.21min.
35.0mg,76％yield,96％ee.[α]D 27＝-153.5(c＝0.1丙酮).1H NMR(400MHz,CD2Cl2)δ8.47-8.39(m,1H),7.91(d,J＝8.0Hz,1H),7.65-7.51(m,3H),7.44-7.36(m,3H),7.24-7.03(m,6H),4.42(d,J＝2.4Hz,1H),4.00(s,5H),3.74(d,J＝2.4Hz,1H),2.19(s,3H).13C NMR(101MHz,CD2Cl2)δ158.6,149.1,141.3(J＝11.4Hz),139.3(J＝11.2Hz),136.1(J＝21.8Hz),135.7,132.9(J＝18.0Hz),129.8(J＝7.7Hz),128.5(J＝5.6Hz),128.3,126.6(J＝8.2Hz),121.7,92.8(J＝12.3Hz),87.9(J＝3.2Hz),76.7(J＝10.6Hz),73.1,72.2,70.9(J＝4.3Hz),15.3.31P NMR(162MHz,CD2Cl2)δ-20.3.IR(薄膜):νmax(cm-1)＝2975,2922,2901,1583,1559,1475,1452,1431,1409,1394,1375,1273,1239,1148,1103,1085,1068,1053,1027,1001,833,814,788,742,714,694,662,607.HRMS(ESI)计算值C28H25[56Fe]NP[M+H]+:462.1069.实测值:462.1066.手性柱Daicel Chiralpak AD-H(4.6×250mm),Hexanes/EtOH/Ethanolamine＝95/05/0.05,0.7mL/min,λ＝280nm,t(minor)＝3.48min,t(major)＝4.86min.
实施例64
将配体(Rp)-VI-4(3.7mg,0.008mmol,96％ee)和[Pd(C3H5)Cl]2(2.9mg,0.008mmol)在无水二氯甲烷(2.0mL)中的混合物在室温下搅拌0.5h，向所得黄色溶液中加入VII(50.4mg,0.2mmol)。再搅拌10分钟后，加入丙二酸二甲酯(79.0mg,0.6mmol)、BSA(122.0mg,0.6mmol)和KOAc(1.0mg,0.008mmol)，反应在室温下搅拌。反应完成后(通过TLC监测)，反应体系用饱和氯化铵淬灭并用乙醚萃取。合并有机层用饱和食盐水洗涤，用无水硫酸钠干燥并过滤。减压旋除溶剂后，将残余物通过柱层析(石油醚/乙酸乙酯＝10/1,v/v)纯化得到VIII。无色液体,58.3mg,90％yield,95％ee.[α]D 27＝+22.0(c＝1.8二氯甲烷).1HNMR(400MHz,CDCl3)δ7.34-7.17(m,10H),6.48(d,J＝15.6Hz,1H),6.33(dd,J＝16.0,8.8Hz,1H),4.27(dd,J＝10.8,8.4Hz,1H),3.95(d,J＝10.8Hz,1H),3.70(s,3H),3.51(s,3H).手性柱Daicel Chiralpak AD-H(4.6×250mm),正己烷/异丙醇＝95/05,1.0mL/min,λ＝254nm,t(major)＝12.42min,t(minor)＝17.75min.
实施例65
在室温下氩气条件下加入AgOAc(1.7mg,0.01mmol,96％ee)，(Rp)-VII-4(5.6mg,0.012mmol)和二氯甲烷(2.0mL)中的搅拌30分钟进行预制备。然后将亚胺IX(51.0mg,0.2mmol)、N-苯基马来酰亚胺X(42.0mg,0.24mmol)和三乙胺(6.0μL,0.04mmol)随后添加到催化剂悬浮液中。反应在室温下搅拌，反应完成后(通过TLC监测)，反应混合物用饱和食盐水淬灭并用乙酸乙酯萃取。合并的有机层用饱和食盐水洗涤，无水硫酸钠干燥并过滤。减压除去溶剂后，残余物通过柱层析(石油醚/乙酸乙酯＝3/1,v/v)纯化得到XI。无色液体,142.3mg,80％yield,98％ee.[α]D 27＝+214.4(c＝1.35DCM).1H NMR(400MHz,氯仿)δ7.47(d,J＝8.4Hz,2H),7.43-7.36(m,2H),7.35-7.30(m,3H),7.16-7.08(m,2H),4.51(d,J＝8.8Hz,1H),4.09(d,J＝6.4Hz,1H),3.85(s,3H),3.72-3.65(m,1H),3.51(t,J＝8.4Hz,1H).手性柱Daicel Chiralpak AD-H(4.6×250mm),正己烷/异丙醇＝50/50,1.0mL/min,λ＝254nm,t(minor)＝13.77min,t(major)＝26.97min.
实施例66
参照实施例1制备。
实施例67：化合物I-45的单晶衍射实验
1.单晶培养：将实施例46中手性柱分离得到的主要组分化合物I-45(100mg)溶于无水乙酸乙酯(20mL)中，加入到2个25mL单口锥形瓶中，-20℃静置5-10天，有单晶析出，收集单晶进行单晶衍射测试.
2.测试参数如下表所示：
3.测定结果：化合物I-45的构型由单晶衍射确定为Sp构型。
实施例68：原料合成rac-II-1
在-78℃下，将nBuLi(2.5M in pentane,2.0equiv)缓慢加入到吡啶二茂铁原料(1.0equiv)的四氢呋喃(5.0mL)溶液的干燥烧瓶中。在-78℃下搅拌4小时。然后加入相应的亲电试剂(2.0equiv)。5分钟后，将混合物升温至室温再搅拌1小时。然后，反应加入氢氧化钠溶液(20mL,2.0M)淬灭。混合物用乙酸乙酯(20mL×3)萃取。合并有机相用饱和食盐水洗涤并用无水硫酸钠干燥。过滤后，减压除去溶剂。粗产物通过硅胶柱层析(己烷/乙酸乙酯＝20/1,v/v)得到产物。
使用的亲电试剂为碘甲烷。
消旋体产物rac-II-1，深红色液体,1.7g,62％yield,5.0mmol scale.1H NMR(400MHz,CD2Cl2)δ8.51(d,J＝5.6Hz,1H),7.62(td,J＝7.6,1.6Hz,1H),7.59-7.55(m,1H),7.10(ddd,J＝6.8,5.2,1.2Hz,1H),4.69-4.67(m,1H),4.29(m,1H),4.22(t,J＝2.8Hz,1H),4.01(s,5H),2.34(s,3H).13C NMR(101MHz,CD2Cl2)δ160.9,149.6,136.3,123.0,121.1,84.29,84.25,72.9,71.0,69.8,67.8,16.0.IR(neat):νmax(cm-1)＝2972,2916,1584,1562,1488,1449,1413,1376,1289,1264,1216,1150,1103,1066,1041,1000,955,880,813,785,740,708,645,618.HRMS(ESI)calcd for C16H16[56Fe]N[M+H]+:278.0627.Found:278.0636.
HPLC:Daicel Chiralcel OD-H(4.6×250mm),Hexanes/IPA＝90/10,1.0mL/min,λ＝286nm,t＝8.34min,t＝12.41min.
HPLC分析显示，在没有手性因素的条件下，产物为消旋体。下同。
实施例69：原料合成rac-II-3
操作同实施例68，使用的亲电试剂为碘乙烷。
消旋体产物rac-II-3，1H NMR(400MHz,CDCl3)δ8.54(d,J＝4.8Hz,1H),7.61-7.52(m,2H),7.10-7.06(m,1H),4.69(s,1H),4.30(s,1H),4.24(s,1H),4.03(s,5H),2.91-2.70(m,2H),1.23(t,J＝7.6Hz,3H).13C NMR(101MHz,CDCl3)δ160.1,148.9,135.4,122.3,120.3,90.4,83.1,70.0,69.6,68.9,67.0,22.2,14.9.IR(neat):νmax(cm-1)＝3089,2964,2920,1584,1563,1487,1452,1415,1372,1316,1292,1263,1234,1213,1150,1104,1087,1069,1045,998,938,880,812,784,740,708,690,635,610.HRMS(ESI)calcd for C17H18[56Fe]N[M+H]+:292.0783.Found:292.0790.
HPLC:Daicel Chiralcel OJ-H(4.6×250mm),Hexanes/IPA＝95/05,1.0mL/min,λ＝254nm,t＝5.80min,t＝7.42min.
实施例70：原料合成rac-II-28
步骤1：在0℃下，向2,2,6,6-四甲基哌啶(1.3equiv)的四氢呋喃(5.0mL)溶液中加入nBuLi(2.5M in pentane,1.2equiv)。搅拌15分钟后，在-30℃将混合物加入到单溴二茂铁(1.0equiv)的四氢呋喃(5.0mL)溶液中，在该温度下搅拌4小时。随后，加入相应的TMSCl(2.0equiv)。5分钟后，混合物升温至室温并搅拌1小时。然后，反应加入氢氧化钠溶液(20mL,2.0M)淬灭。混合物用乙酸乙酯(20mL x 3)萃取。合并有机相用饱和食盐水洗涤并用无水硫酸钠干燥。过滤后，减压除去溶剂。粗产物通过硅胶柱层析(己烷/乙酸乙酯＝30/1,v/v)得到中间体1(消旋体)。
步骤2：在0℃下，向2,2,6,6-四甲基哌啶(1.3equiv)的四氢呋喃(5.0mL)溶液中加入nBuLi(2.5M in pentane,1.2equiv)。搅拌15分钟后，在-30℃将混合物加入到中间体1(1.0equiv)的四氢呋喃(5.0mL)溶液中，在该温度下搅拌4小时。然后，加入氯化锌(1.0M inTHF,2.0equiv)。5分钟后，混合物升温至室温并搅拌1小时。将Pd(PPh3)4(5mol％)和2-碘吡啶(3.0equiv)添加到上述二茂铁锌试剂中。然后，反应加入氢氧化钠溶液(20mL,2.0M)淬灭。混合物用乙酸乙酯(20mL×3)萃取。合并有机相用饱和食盐水洗涤并用无水硫酸钠干燥。过滤后，减压除去溶剂。粗产物通过硅胶柱层析(己烷/乙酸乙酯＝30/1,v/v)得到中间体2(消旋体)。
步骤3：在-78℃下，将nBuLi(2.5M in pentane,1.2equiv)缓慢添加到中间体2的四氢呋喃(5.0mL)溶液的干燥烧瓶中。在该温度下搅拌2小时。随后，加入H2O(2.0equiv)。5分钟后，混合物升温至室温并再搅拌1小时。然后，反应加入氢氧化钠溶液(20mL,2.0M)淬灭。混合物用乙酸乙酯(20mL×3)萃取。合并有机相用饱和食盐水洗涤并用无水硫酸钠干燥。过滤后，减压除去溶剂。粗产物通过硅胶柱层析(己烷/乙酸乙酯＝30/1,v/v)得到产物。
消旋体产物rac-II-28，1H NMR(400MHz,CD2Cl2)δ8.48(dd,J＝4.0,1.2Hz,1H),7.61(td,J＝7.6,2.0Hz,1H),7.46(d,J＝8.0Hz,1H),7.09(ddd,J＝7.2,4.8,1.2Hz,1H),5.06(dd,J＝2.8,1.6Hz,1H),4.89(d,J＝1.6Hz,1H),4.36-4.34(m,1H),4.01(s,5H),0.29(s,9H).13C NMR(101MHz,CD2Cl2)δ159.8,150.0,136.7,121.3,120.9,87.4,75.5,73.0,70.8,70.6,0.2.IR(薄膜):νmax(cm-1)＝2954,1601,1556,1494,1441,1408,1382,1307,1244,1203,1136,1104,1051,999,909,863,830,809,750,690,633.HRMS(ESI)计算值C18H22[56Fe]NSi[M+H]+:336.0865.实测值:336.0864.
HPLC:Daicel Chiralcel OJ-3(SFC:3.0mm,I.D.:150mm),CO2/MeOH＝90/10,1.0mL/min,λ＝214nm,t＝5.72min,t＝6.18min.
实施例71：原料合成rac-II-30
在0℃下，向2,2,6,6-四甲基哌啶(1.3equiv)的四氢呋喃(5.0mL)溶液中加入nBuLi(2.5M in pentane,1.2equiv)。搅拌15分钟后，在-30℃将混合物加入到单溴二茂铁(1.0equiv)的四氢呋喃(5.0mL)溶液中，在该温度下搅拌4小时。随后，加入氯化锌(1.0M inTHF,2.0equiv)。5分钟后，混合物升温至室温并搅拌1小时。将Pd(PPh3)4(5mol％)和对甲氧基溴苯(3.0equiv)加入到上述二茂铁锌试剂中。然后，反应加入氢氧化钠溶液(20mL,2.0M)淬灭。混合物用乙酸乙酯(20mL×3)萃取。合并有机相用饱和食盐水洗涤并用无水硫酸钠干燥。过滤后，减压除去溶剂。粗产物通过硅胶柱层析(己烷/乙酸乙酯＝30/1,v/v)得到中间体1(消旋体)。
后续操作同实施例70中步骤2和3
1H NMR(400MHz,CD2Cl2)δ8.49(ddd,J＝4.8,2.0,0.8Hz,1H),7.62(td,J＝8.0,2.0Hz,1H),7.54-7.47(m,3H),7.10(ddd,J＝7.2,4.8,1.2Hz,1H),6.89(d,J＝8.8Hz,2H),5.40(t,J＝1.6Hz,1H),5.04(dd,J＝2.8,1.6Hz,1H),4.84(dd,J＝2.8,1.6Hz,1H),3.91(s,5H),3.83(s,3H).13C NMR(101MHz,CD2Cl2)δ159.8,159.2,150.0,136.7,131.4,128.0,121.3,120.7,114.7,88.4,85.0,71.8,68.6,68.4,66.0,56.0.IR(薄膜):νmax(cm-1)＝2970,2918,1609,1584,1562,1524,1498,1454,1439,1417,1288,1264,1243,1176,1147,1104,1045,1027,1000,894,827,809,784,742,700,648.HRMS(ESI)计算值C22H20[56Fe]NO[M+H]+:370.0889.实测值:370.0888.
HPLC:Daicel Phenomenex Lux 5u Cellulose-2(4.6×250mm),Hexanes/IPA＝70/30,0.7mL/min,λ＝254nm,t＝9.50min,t＝12.21min.
实施例72：手性1，3二茂铁II-30的应用
在-78℃下，向1，3二茂铁II-30(1.0equiv)的乙醚溶液中加入叔丁基锂(1.5equiv)。将反应混合物在-78℃搅拌4小时。然后加入相应的二苯基膦氯(1.5equiv)。之后，将混合物升温至室温并搅拌过夜。将反应混合物用冰冷的水淬灭并用乙酸乙酯萃取。合并的有机层用盐水洗涤，用无水硫酸钠干燥并过滤。减压除去溶剂后，残余物经硅胶柱层析(石油醚/乙酸乙酯＝20/1,v/v)纯化得到VI-5。HRMS(ESI)计算值C34H29[56Fe]NOP[M+H]+:554.1331.实测值:554.1332.
将配体VI-5(4.43mg,0.008mmol)和[Pd(C3H5)Cl]2(2.9mg,0.008mmol)在无水二氯甲烷(2.0mL)中的混合物在室温下搅拌0.5h，向所得黄色溶液中加入VII(50.4mg,0.2mmol)。再搅拌10分钟后，加入丙二酸二甲酯(79.0mg,0.6mmol)、BSA(122.0mg,0.6mmol)和KOAc(1.0mg,0.008mmol)，反应在室温下搅拌。反应完成后(通过TLC监测)，反应体系用饱和氯化铵淬灭并用乙醚萃取。合并有机层用饱和食盐水洗涤，用无水硫酸钠干燥并过滤。减压旋除溶剂后，将残余物通过柱层析(石油醚/乙酸乙酯＝10/1,v/v)纯化得到VIII。无色液体,58.3mg,90％yield,96％ee.
实施例73：II’-1和I’-1的制备
为的消旋体。
在完全干燥的10mL Schlenk管中加入LiOtBu(48.0mg,0.6mmol)、(S,S)-P6’(25.3mg,0.04mmol)、[Rh(C2H4)2Cl]2(3.9mg,0.01mmol)、rac-II(0.2mmol,1.0equiv)和对甲氧基溴苯(0.4mmol,2.0equiv)。将体系抽换氩气三次，然后加入四氢呋喃(2.0mL)。加热至60℃反应8-23小时，过滤，减压除去溶剂，柱层析纯化(石油醚/乙酸乙酯＝20/1,v/v)。
34.4mg,45％yield,96％ee.分析数据:[α]D 27＝-259.9(c＝0.1丙酮).HRMS(ESI)计算值C23H22[56Fe]NO[M+H]+:384.1045.实测值:384.1046.手性柱Daicel Chiralcel OD-H(4.6×250mm),正己烷/异丙醇＝95/05,0.7mL/min,λ＝286nm,t(major)＝10.99min,t(minor)＝11.55min.
24.8mg,45％yield,97％ee.分析数据:[α]D 29＝+89.7(c＝0.1丙酮).计算值C16H16[56Fe]N[M+H]+:278.0627.实测值:278.0636.手性柱Daicel Chiralcel OD-H(4.6×250mm),正己烷/异丙醇＝90/10,1.0mL/min,λ＝286nm,t(major)＝8.31min,t(minor)＝12.31min.
在此基础上，本发明开发了所述的由消旋底物使用手性配体进行选择性反应，从而拆分得到特定的平面手性茂金属化合物。采用本发明的制备方法可以较高收率和较高手性纯度的得到1,3-二取代、1,2,3-三取代、1,2,4-三取代、四取代平面手性茂金属化合物。该平面手性茂金属原料可以用于进一步制备手性配体，在不对称催化中开发出更广泛的应用。
Claims (17)
1.一种平面手性茂金属化合物的制备方法，其特征在于，其包括以下步骤：保护气体氛围下，在有机溶剂中，在手性膦配体、铑催化剂和碱的存在下，将如式rac-II所示消旋化合物与如式III所示化合物进行如下所示的芳基化反应，分别得到平面手性茂金属化合物；
或者
其中，X独立地为卤素；
R1、R2和R3独立地为H、F、Cl、Br、I、C1-C10的烷基、C1-C10的烷基-O-或苯基；
或者，R1、R2和R3中任意两个相邻的基团相连，与其所连接的碳共同形成苯基；
R4和R5独立地为H、F、Cl、Br、I、C1-C10的烷基、C1-C10的烷基-O-、C2-C10的烯基、C2-C10的炔基、C1-C10的烷基-S-、三个C1-C10的烷基取代的硅基或苯基，或者，被1、2或3个Ra基团取代的：C1-C10的烷基、C1-C10的烷基-O-、C2-C10的烯基、C2-C10的炔基、C1-C10的烷基-S-或苯基；
所述的Ra独立地为D、C1-C10的烷基、C1-C10的烷基-O-或C3-C10的环烷基；且R4和R5不同时为H；
R6独立地为H或R6a-L1-；
R6a独立地为H、未取代或被一个或多个R6a-1取代的C1-C10的脂烃基或被三个C1-C10的烷基取代的硅基；
R7独立地为未取代或被一个或多个R7-1取代的C6-C12的芳基、或未取代或被一个或多个R7-2取代的5-12元的杂芳基；所述的5-12元的杂芳基中，杂原子选自N、O和S中的一种或多种，杂原子个数为1-4个；当所述的取代基个数为多个时，相同或不同；
R7-1和R7-2独立地为F、Cl、Br、I、硝基、氰基、或R7a-L2；
或者，当R7-1和R7-2独立地为多个时，任意两个相邻基团连接，与其所连接的原子共同形成C3-C6的脂环烃基或C3-C5的杂脂环烃基；所述的C3-C5的杂脂环烃基中，杂原子选自N、O和S中的一种或多种，杂原子个数为1-2个；
L1独立地为连接键；
L2独立地为连接键、C1-C6的亚烷基、-(C1-C6的亚烷基)-O-、-O-、-S-、-C(＝O)-、-C(＝O)O-、-N(RL)-或-S(＝O)2-；
RL独立地为H或C1-C6的烷基；
R7a独立地为H、未取代或被一个或多个R7a-1取代的C1-C6的烷基、或未取代或被一个或多个R7a-2取代的苯基；
R6a-1、R7a-1和R7a-2独立地为C1-C6的烷基；
M独立地为Fe和Ru；
所述的铑催化剂为[Rh(C2H4)2Cl]2、[Rh(CO)2Cl]2和[Rh(cod)Cl]2中的一种或多种；
所述的手性膦配体为 所示的酒石酸衍生的亚磷酸酯配体；其中，R8和R8’独立地为未取代或被一个或多个R8-1取代的苯基，R9和R9’独立地为NR9-1R9-2或者未取代或被一个或多个R9-3取代的苯基，R8-1和R9-3独立地为三氟甲基、C1-C4的烷基或C1-C4的烷基-O-，R9-1和R9-2独立地为C1-C4的烷基；
当所述的手性膦配体为所示的酒石酸衍生的亚磷酸酯配体时，制备得到如式II和/或式I所示的手性茂金属化合物；
当所述的手性膦配体为所示的酒石酸衍生的亚磷酸酯配体时，制备得到如式II’和/或式I’所示的手性茂金属化合物。
2.如权利要求1所述的平面手性茂金属化合物的制备方法，其特征在于，其满足如下条件中的一种或多种：
(1)Ra、R1、R2和R3独立地为C1-C10的烷基和C1-C10的烷基-O-里的C1-C10的烷基独立地为甲基、乙基、丙基、丁基、戊基或己基；
(2)R4和R5独立地为C1-C10的烷基、被取代的C1-C10的烷基、C1-C10的烷基-O-、被取代的C1-C10的烷基-O-、C1-C10的烷基-S-、被取代的C1-C10的烷基-S-、被三个C1-C10的烷基取代的硅基里的C1-C10的烷基独立地为甲基、乙基、丙基、丁基、戊基或己基；
(3)所述的未取代或被一个或多个R6a-1取代的C1-C10的脂烃基里的C1-C10的脂烃基独立地为C1-C10的烷基、C2-C10的烯基或C2-C10的炔基；
(4)所述的R6a独立地为三个C1-C10的烷基取代的硅基里的C1-C10的烷基独立地为甲基、乙基、丙基、丁基、戊基或己基；
(5)所述的未取代或被一个或多个R7-1取代的C6-C12的芳基里的C6-C12的芳基独立地为苯基、茚基或萘基；
(6)所述的未取代或被一个或多个R7-2取代的5-12元的杂芳基里的5-12元的杂芳基中，杂原子选自N、O和S中的一种或多种，杂原子个数为1-2个；
(7)所述的被一个或多个R7-1取代的C6-C12的芳基中，R7-1的个数为1、2、3或4个；
(8)所述的被一个或多个R7-2取代的5-12元的杂芳基中，R7-2的个数为1、2、3或4个；
(9)当R7-1和R7-2独立地为多个，任意两个相邻基团连接，与其所连接的原子共同形成C3-C6的脂环烃基时，所述的C3-C6的脂环烃基独立地为环丙基、环丁基、环戊基或环己基；
(10)当R7-1和R7-2独立地为多个，任意两个相邻基团连接，与其所连接的原子共同形成C3-C5的杂脂环烃基时，所述的C3-C5的杂脂环烃基独立地为C3-C5的杂环烷基或C3-C5的杂环烯基；
(11)L2独立地为C1-C6的亚烷基或-(C1-C6的亚烷基)-O-里的C1-C6的亚烷基独立地为-CH2-、-CH2CH2-、-CH(CH3)-、-CH(CH3)CH2-或-C(CH3)2-；
(12)RL独立地为C1-C6的烷基里的C1-C6的烷基独立地为甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基或叔丁基；
(13)R7a独立地为未取代或被一个或多个R7a-1取代的C1-C6的烷基里的C1-C6的烷基独立地为甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基或叔丁基；
(14)所述的R7a-1取代的个数为1、2、3或4个；
(15)R6a-1和R7a-1独立地为C1-C6的烷基里的C1-C6的烷基独立地为甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基或叔丁基；
(16)X为F、Cl、Br或I。
3.如权利要求2所述的平面手性茂金属化合物的制备方法，其特征在于，其满足如下条件中的一种或多种：
(1)Ra、R1、R2和R3独立地为C1-C10的烷基和C1-C10的烷基-O-里的C1-C10的烷基独立地为甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基或叔丁基；
(2)R4和R5独立地为C1-C10的烷基、被取代的C1-C10的烷基、C1-C10的烷基-O-、被取代的C1-C10的烷基-O-、C1-C10的烷基-S-、被取代的C1-C10的烷基-S-、被三个C1-C10的烷基取代的硅基里的C1-C10的烷基独立地为甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基或叔丁基；
(3)所述的未取代或被一个或多个R6a-1取代的C1-C10的脂烃基里的C1-C10的脂烃基独立地为甲基、乙基、丙基、丁基、戊基、己基、乙烯基、1-丙烯基、2-丙烯基、烯丙基、1-丁烯基、2-丁烯基、2-甲基烯丙基、2-甲基丙-1-烯-1-基、丁-3-烯-1-基、乙炔基、丙-1-炔基、丙-2-炔基、丁-1-炔基、丁-2-炔基、丁-3-炔基或1-甲基丙-2-炔基；
(4)所述的R6a独立地为三个C1-C10的烷基取代的硅基里的C1-C10的烷基独立地为甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基或叔丁基；
(5)所述的未取代或被一个或多个R7-2取代的5-12元的杂芳基里的5-12元的杂芳基独立地为呋喃基、噻吩基、苯并呋喃基、苯并噻吩基、苯并吡咯基或苯并吡啶基；
(6)当R7-1和R7-2独立地为多个，任意两个相邻基团连接，与其所连接的原子共同形成C3-C5的杂脂环烃基，所述的C3-C5的杂脂环烃基独立地为C3-C5的杂环烷基或C3-C5的杂环烯基时，所述的C3-C5的杂环烷基可独立地为所述的C3-C5的杂环烯基可独立地为
(7)X为Cl或Br。
4.如权利要求3所述的平面手性茂金属化合物的制备方法，其特征在于，所述的未取代或被一个或多个R7-2取代的5-12元的杂芳基里的5-12元的杂芳基独立地为
5.如权利要求1所述的平面手性茂金属化合物的制备方法，其特征在于，其满足如下条件中的一种或两种：
(1)Ra独立地为C3-C10的环烷基里的C3-C10的环烷基独立地为环丙基、环丁基、环戊基或环己基；
(2)R4和R5独立地为C2-C10的烯基、被取代的C2-C10的烯基里的C2-C10的烯基为乙烯基、1-丙烯基、2-丙烯基、烯丙基、1-丁烯基、2-丁烯基、2-甲基烯丙基、2-甲基丙-1-烯-1-基、丁-3-烯-1-基或2-甲基-丙-1-烯-1-基。
6.如权利要求1所述的平面手性茂金属化合物的制备方法，其特征在于，R4和R5独立地为C2-C10的炔基、被取代的C2-C10的炔基里的C2-C10的炔基为乙炔基、丙-1-炔基、丙-2-炔基、丁-1-炔基、丁-2-炔基、丁-3-炔基或1-甲基丙-2-炔基。
7.如权利要求1-6中任一项所述的平面手性茂金属化合物的制备方法，其特征在于，其满足如下条件中的一种或多种：
(1)R1、R2和R3独立地为H、Me、苯基、MeO-或F；
(2)R4和R5独立地为H、Me、Et、nBu、CD3、 TMS、Et3Si、tBuS、F、
(3)R6独立地为H、Me、nBu或iPr；
(4)R7-1和R7-2独立地为F、Cl、Br、I、氰基、甲基、甲基-O-、甲基-S-、-C(＝O)-CH3、-N(CH3)2、苯基或对甲苯磺酰基。
8.如权利要求1-6中任一项所述的平面手性茂金属化合物的制备方法，其特征在于，其满足如下条件中的一种或两种：
(1)R1、R2和R3中任意两个相邻的基团相连时，与其所连接的碳共同形成苯基；
(2)R4为H。
9.如权利要求1-6中任一项所述的平面手性茂金属化合物的制备方法，其特征在于，其满足如下条件中的一种或多种：
(1)R7独立地为
(2)独立地为
(3)独立地为
10.如权利要求1-6中任一项所述的平面手性茂金属化合物的制备方法，其特征在于，所述的如式I、式I’、式II、式II’所示的茂金属化合物分别选自以下任一结构：
11.如权利要求1-6中任一项所述的平面手性茂金属化合物的制备方法，其特征在于，其满足如下条件中的一种或多种：
(1)所述的保护气体为氦气、氖气、氮气和氩气中的一种或多种；
(2)所述的有机溶剂为醚类溶剂和/或芳烃类溶剂；
(3)所述的如式rac-II所示化合物在所述的有机溶剂中的摩尔浓度为0.01-0.5mol/L；
(4)所述的铑催化剂为[Rh(C2H4)2Cl]2；
(5)所述的铑催化剂与所述的如式rac-II所示化合物的摩尔比为0.05-0.2:1；
(6)所述的碱为叔丁醇锂、叔丁醇钠、碳酸钾和碳酸铯中的一种或多种；
(7)所述的碱与所述的如式rac-II所示化合物的摩尔比为1-5:1；
(8)所述的芳基化反应的温度为0-100℃；
(9)所述的手性膦配体与所述的如式rac-II所示化合物的摩尔比为0.02-0.3:1；
(10)所述的手性膦配体为所示的酒石酸衍生的亚磷酸酯配体；其中，R8和R8’独立地为未取代或被一个或多个R8-1取代的苯基，R9和R9’独立地为NR9-1R9-2或者未取代或被一个或多个R9-3取代的苯基，R8-1和R9-3独立地为三氟甲基、C1-C4的烷基或C1-C4的烷基-O-，R9-1和R9-2独立地为C1-C4的烷基；所述的C1-C4的烷基为甲基、乙基、丙基或异丙基；
(11)反应中还加入干燥剂；
(12)其还进一步包括后处理操作，其包括以下步骤：稀释，分离提纯。
12.如权利要求11所述的平面手性茂金属化合物的制备方法，其特征在于，其满足如下条件中的一种或多种：
(1)所述的保护气体为氩气；
(2)所述的有机溶剂为1,4-二氧六环、四氢呋喃和甲苯中的一种或多种；
(3)所述的如式rac-II所示化合物在所述的有机溶剂中的摩尔浓度为0.1-0.5mol/L；
(4)所述的铑催化剂与所述的如式rac-II所示化合物的摩尔比为0.05-0.07:1；
(5)所述的碱与所述的如式rac-II所示化合物的摩尔比为2-4:1；
(6)所述的芳基化反应的温度为50-70℃；
(7)所述的手性膦配体与所述的如式rac-II所示化合物的摩尔比为0.05:1、0.1:1、0.15:1、0.2:1或0.3:1；
(8)反应中还加入干燥的分子筛。
13.如权利要求12所述的平面手性茂金属化合物的制备方法，其特征在于，所述的如式rac-II所示化合物在所述的有机溶剂中的摩尔浓度为0.1-0.2mol/L。
14.如权利要求11所述的平面手性茂金属化合物的制备方法，其特征在于，其满足如下条件中的一种或两种：
(1)所述的所示的酒石酸衍生的亚磷酸酯配体，分别为以下任一结构：
(2)当所述的手性膦配体选自下列化合物中的任一种时，制备得到如式II和/或式I所示的手性茂金属化合物；
当所述的手性膦配体选自下列化合物中的任一种时，制备得到如式II’和/或式I’所示的手性茂金属化合物；
15.一种如式II、式II’所示化合物，其结构如下所示，
其中，R1、R2、R3和R6为H；
M为Fe；
R4和R5独立地为H、乙基、丙基、戊基、己基，或者，被1、2或3个Ra基团取代的苯基；且R4和R5不同时为H；所述的Ra独立地为乙基-O-、丙基-O-、丁基-O-、戊基-O-或己基-O-。
16.一种平面手性吡啶类二茂金属化合物，其结构如式VI-3所示，
其中，R1、R2、R3和R6为H；
M为Fe；
R10为：
R4和R5独立地为H、C1-C10的烷基，或者，被1、2或3个Ra基团取代的苯基；且R4和R5不同时为H；所述的Ra独立地为C1-C10的烷基-O-；Ar1和Ar2独立地为
R10-1、R10-2、R10-3、R10-4和R10-5独立地为H、F、Cl、Br、I或CF3。
17.如权利要求16所述的平面手性吡啶类二茂金属化合物，其特征在于，所述的平面手性吡啶类二茂铁化合物选自如下结构：
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