CN106279292B - Metal iridium complex, monocrystalline, benzindole class compound and synthetic method and application - Google Patents
Metal iridium complex, monocrystalline, benzindole class compound and synthetic method and application Download PDFInfo
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- CN106279292B CN106279292B CN201510305993.8A CN201510305993A CN106279292B CN 106279292 B CN106279292 B CN 106279292B CN 201510305993 A CN201510305993 A CN 201510305993A CN 106279292 B CN106279292 B CN 106279292B
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 52
- 239000002184 metal Substances 0.000 title claims abstract description 52
- 229910052741 iridium Inorganic materials 0.000 title claims abstract description 48
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 title claims abstract description 41
- -1 benzindole class compound Chemical class 0.000 title claims abstract description 29
- 238000010189 synthetic method Methods 0.000 title abstract description 5
- 238000006467 substitution reaction Methods 0.000 claims abstract description 30
- 239000003960 organic solvent Substances 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 10
- 125000000746 allylic group Chemical group 0.000 claims abstract description 6
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims description 184
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 161
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 93
- 239000002904 solvent Substances 0.000 claims description 81
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 56
- 229910052736 halogen Inorganic materials 0.000 claims description 36
- 150000002367 halogens Chemical class 0.000 claims description 36
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 30
- 229910052799 carbon Inorganic materials 0.000 claims description 30
- 125000000217 alkyl group Chemical group 0.000 claims description 23
- 125000001424 substituent group Chemical group 0.000 claims description 21
- 239000002585 base Substances 0.000 claims description 20
- 239000000460 chlorine Substances 0.000 claims description 18
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 15
- 125000003545 alkoxy group Chemical group 0.000 claims description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 14
- 239000013078 crystal Substances 0.000 claims description 13
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 12
- 229910052731 fluorine Inorganic materials 0.000 claims description 12
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 12
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 12
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 12
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 12
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 10
- 239000003513 alkali Substances 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 10
- 229910052794 bromium Inorganic materials 0.000 claims description 10
- 229910052801 chlorine Inorganic materials 0.000 claims description 10
- 150000008282 halocarbons Chemical class 0.000 claims description 10
- 150000007529 inorganic bases Chemical class 0.000 claims description 10
- 229910052740 iodine Inorganic materials 0.000 claims description 10
- 150000007530 organic bases Chemical class 0.000 claims description 10
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 10
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 9
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-Lutidine Substances CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 8
- 150000004696 coordination complex Chemical class 0.000 claims description 8
- 150000002825 nitriles Chemical class 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 8
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 claims description 7
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical group [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 7
- 239000011737 fluorine Substances 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 6
- 150000001408 amides Chemical class 0.000 claims description 6
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 6
- 125000005913 (C3-C6) cycloalkyl group Chemical group 0.000 claims description 5
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 5
- 238000010668 complexation reaction Methods 0.000 claims description 5
- 239000011630 iodine Substances 0.000 claims description 5
- 150000002503 iridium Chemical class 0.000 claims description 5
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 5
- 229910052701 rubidium Inorganic materials 0.000 claims description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 4
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 4
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 4
- 229960001701 chloroform Drugs 0.000 claims description 4
- 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 4
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 4
- LZWQNOHZMQIFBX-UHFFFAOYSA-N lithium;2-methylpropan-2-olate Chemical compound [Li+].CC(C)(C)[O-] LZWQNOHZMQIFBX-UHFFFAOYSA-N 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 4
- 229910017488 Cu K Inorganic materials 0.000 claims description 3
- 229910017541 Cu-K Inorganic materials 0.000 claims description 3
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-diisopropylethylamine Substances CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 230000005855 radiation Effects 0.000 claims description 3
- 238000004467 single crystal X-ray diffraction Methods 0.000 claims description 3
- 238000001228 spectrum Methods 0.000 claims description 3
- 125000006656 (C2-C4) alkenyl group Chemical group 0.000 claims description 2
- FTTATHOUSOIFOQ-UHFFFAOYSA-N 1,2,3,4,6,7,8,8a-octahydropyrrolo[1,2-a]pyrazine Chemical compound C1NCCN2CCCC21 FTTATHOUSOIFOQ-UHFFFAOYSA-N 0.000 claims description 2
- 125000004973 1-butenyl group Chemical group C(=CCC)* 0.000 claims description 2
- 125000006017 1-propenyl group Chemical group 0.000 claims description 2
- 125000004974 2-butenyl group Chemical group C(C=CC)* 0.000 claims description 2
- XWKFPIODWVPXLX-UHFFFAOYSA-N 2-methyl-5-methylpyridine Natural products CC1=CC=C(C)N=C1 XWKFPIODWVPXLX-UHFFFAOYSA-N 0.000 claims description 2
- 125000004975 3-butenyl group Chemical group C(CC=C)* 0.000 claims description 2
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 2
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 229910001914 chlorine tetroxide Inorganic materials 0.000 claims description 2
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 2
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 claims description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 2
- 125000002510 isobutoxy group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])O* 0.000 claims description 2
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 2
- 125000006606 n-butoxy group Chemical group 0.000 claims description 2
- 125000003506 n-propoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])O* 0.000 claims description 2
- 125000001624 naphthyl group Chemical group 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 2
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 2
- 235000011009 potassium phosphates Nutrition 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 2
- 239000012312 sodium hydride Substances 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 150000002431 hydrogen Chemical group 0.000 claims 3
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 38
- 230000000694 effects Effects 0.000 abstract description 9
- 150000003852 triazoles Chemical class 0.000 abstract description 7
- 239000003446 ligand Substances 0.000 abstract description 6
- 238000012805 post-processing Methods 0.000 abstract 1
- 150000003839 salts Chemical class 0.000 abstract 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 154
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 106
- 239000007787 solid Substances 0.000 description 73
- 238000005160 1H NMR spectroscopy Methods 0.000 description 33
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical group CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 33
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 28
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 19
- 239000003208 petroleum Substances 0.000 description 17
- 125000001072 heteroaryl group Chemical group 0.000 description 16
- 238000004440 column chromatography Methods 0.000 description 13
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 12
- 229910052786 argon Inorganic materials 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- YMWUJEATGCHHMB-DICFDUPASA-N dichloromethane-d2 Chemical compound [2H]C([2H])(Cl)Cl YMWUJEATGCHHMB-DICFDUPASA-N 0.000 description 10
- 238000004809 thin layer chromatography Methods 0.000 description 10
- 0 *C(C(*)N(*)C1)N(C2C3(*=C)C4=CCCC44C3=CC4)C1=NN2*1=CC1 Chemical compound *C(C(*)N(*)C1)N(C2C3(*=C)C4=CCCC44C3=CC4)C1=NN2*1=CC1 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 9
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- 239000012043 crude product Substances 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 238000000921 elemental analysis Methods 0.000 description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 5
- 238000001953 recrystallisation Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000004293 19F NMR spectroscopy Methods 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000003480 eluent Substances 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- 239000012454 non-polar solvent Substances 0.000 description 3
- 239000002798 polar solvent Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- ADLVDYMTBOSDFE-UHFFFAOYSA-N 5-chloro-6-nitroisoindole-1,3-dione Chemical compound C1=C(Cl)C([N+](=O)[O-])=CC2=C1C(=O)NC2=O ADLVDYMTBOSDFE-UHFFFAOYSA-N 0.000 description 2
- 229910020323 ClF3 Inorganic materials 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
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- 230000000052 comparative effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
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- OAYLNYINCPYISS-UHFFFAOYSA-N ethyl acetate;hexane Chemical compound CCCCCC.CCOC(C)=O OAYLNYINCPYISS-UHFFFAOYSA-N 0.000 description 2
- ANFZRGMDGDYNGA-UHFFFAOYSA-N ethyl acetate;propan-2-ol Chemical compound CC(C)O.CCOC(C)=O ANFZRGMDGDYNGA-UHFFFAOYSA-N 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005650 intramolecular substitution reaction Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
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- 238000001308 synthesis method Methods 0.000 description 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- VYXHVRARDIDEHS-UHFFFAOYSA-N 1,5-cyclooctadiene Chemical compound C1CC=CCCC=C1 VYXHVRARDIDEHS-UHFFFAOYSA-N 0.000 description 1
- 239000004912 1,5-cyclooctadiene Substances 0.000 description 1
- HIYWOHBEPVGIQN-UHFFFAOYSA-N 1h-benzo[g]indole Chemical class C1=CC=CC2=C(NC=C3)C3=CC=C21 HIYWOHBEPVGIQN-UHFFFAOYSA-N 0.000 description 1
- 125000005915 C6-C14 aryl group Chemical group 0.000 description 1
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- QIQOGKFBSVGIKZ-LBMMBOJWSA-N CC(C1N(c2c(C)cc(C)cc2C)N=C(CN(C2)C(C(F)(F)F)=O)N1[C@H]2c1ccccc1)(C1=CCC11C=CCC1)Cl Chemical compound CC(C1N(c2c(C)cc(C)cc2C)N=C(CN(C2)C(C(F)(F)F)=O)N1[C@H]2c1ccccc1)(C1=CCC11C=CCC1)Cl QIQOGKFBSVGIKZ-LBMMBOJWSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- KUXDQQMEFBFTGX-UHFFFAOYSA-N [N].P Chemical compound [N].P KUXDQQMEFBFTGX-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 229940125890 compound Ia Drugs 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- SPWVRYZQLGQKGK-UHFFFAOYSA-N dichloromethane;hexane Chemical compound ClCCl.CCCCCC SPWVRYZQLGQKGK-UHFFFAOYSA-N 0.000 description 1
- WGLUMOCWFMKWIL-UHFFFAOYSA-N dichloromethane;methanol Chemical compound OC.ClCCl WGLUMOCWFMKWIL-UHFFFAOYSA-N 0.000 description 1
- BLEBFDYUDVZRFG-UHFFFAOYSA-N dichloromethane;propan-2-ol Chemical compound ClCCl.CC(C)O BLEBFDYUDVZRFG-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002504 iridium compounds Chemical class 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
Abstract
The invention discloses a kind of metal iridium complex, monocrystalline, benzindole class compound and synthetic method and applications.This method comprises the steps of in organic solvent, in the presence of base, by chiral triazole Cabbeen salt respectively with [Ir (cod) X1]2、[Ir(cod)X1a]2、[Ir(cod)X1b]2、[Ir(cod)X1c]2、[Ir(cod)X1d]2Or [Ir (cod) X1e]2Carry out complex reaction.Application the invention also discloses metal iridium complex as catalyst in asymmetric allylic substitution.For metal iridium complex of the invention using triazole Cabbeen as ligand, synthetic method and post-processing are simple, and have extraordinary effect in the asymmetric allylic substitution of metal iridium catalysis.
Description
Technical Field
The invention relates to a metal iridium complex, a single crystal, a benzindole compound, a synthetic method and application.
Background
The asymmetric allyl substitution reaction catalyzed by the iridium metal can construct carbon-carbon bonds and carbon-hybrid bonds with high enantioselectivity and regioselectivity, and is widely applied to synthesis. The catalysts used in the reactions are mainly[Ir(cod)Cl]2And chiral phosphine nitrogen ligands [ (a) Miyabe, h.; Takemoto, y.synlett2005,1641.(b) Takeuchi, r.; Kezuka, s.synthes 2006,3349.(c) Helmchen, g.; Dahnz, a.; D ü bon, p.; Schelwies, m.; Weihofen, r.chem.commun.2007,675.(D) Helmchen chen, g.; Iridium compounds In organic Synthesis; 2, l.a.; lever, c.eds.; wil VCH: Weinheim, german, 2009; p211.(e) Hartwig, f.; stanly, l.m.chem.s.r., usa, 2011, r.7, p.g., Hartwig, r.f.;, chen, l.m.r.26, r.7. org, p.g.;, r. t. p. t. g.; r.p.g. 7, r.g., r.7. org, r.p.g.]. The N-heterocyclic carbene can be used as a good metal ligand to be applied to catalytic reaction as same as a phosphine ligand due to the strong sigma electron-donating capability and the unique spatial structure of the N-heterocyclic carbene. Compared with common imidazole carbene, imidazoline carbene and thiazole carbene, the triazole carbene has less application in metal catalysis due to the weak electron donating capability. In particular, the use of chiral triazole carbenes as ligands in allyl substitution reactions has not been reported in the literature to date.
Disclosure of Invention
The invention aims to provide a metal iridium complex, a single crystal and a benzo indole compound which are completely different from the prior art, a synthetic method and application thereof. The metal iridium complex takes triazole carbene as a ligand, has simple synthesis method and post-treatment, and has good effect in the allyl substitution reaction catalyzed by metal iridium. Therefore, the metal iridium complex has very important significance for the expansion of the type of the metal iridium-catalyzed allyl substitution reaction catalyst and the abundance of the reaction types, and a class of benzindole compounds is prepared in the metal iridium-catalyzed allyl substitution reaction.
The invention provides a metal iridium complex shown in a general formula I, a general formula II, a general formula III, a general formula IV, a general formula V or a general formula VI, wherein carbon marked by x is chiral carbon or non-chiral carbon, and when the carbon is chiral carbon, the chiral carbon is in an S configuration or an R configuration;
in the general formulae I to VI, R1、R1a、R1b、R1c、R1dAnd R1eIndependently is C1-C8Alkyl of (C)3-C6Cycloalkyl of, C1-C8Perfluoroalkyl group of (1), substituted or unsubstituted C6-C20Or substituted or unsubstituted C2-C20The heteroaryl group of (a);
R2、R2’、R2a、R2a’、R2b、R2b’、R2cand R2c’Independently of one another is hydrogen, C1-C8Alkyl of (C)3-C6Cycloalkyl of, C1-C8Perfluoroalkyl group of (1), substituted or unsubstituted C6-C20Or substituted or unsubstituted C2-C20The heteroaryl group of (a); or R2And R2’And the carbon atoms to which they are attached together form C5-C8Cycloalkyl groups of (a);
R3is composed ofWherein R isaIs C1-C8Alkyl of (C)1-C8Perfluoroalkyl group of (1), substituted or unsubstituted C6-C20Or substituted or unsubstituted C2-C20The heteroaryl group of (a); rbIs C1-C8Alkyl of (C)1-C8Alkoxy group of (C)1-C8Perfluoroalkyl group of (1), substituted or unsubstituted C6-C20Aryl of (2), or substituted or unsubstituted C2-C20The heteroaryl group of (a);
R4、R4aand R4bIndependently of one another is hydrogen, C1-C8Alkyl orWherein R isc、Rc' and Rc"independently is C1-C8Alkyl groups of (a);
R5is hydrogen, halogen, C1-C8Alkyl of (C)3-C6Cycloalkyl of, C1-C8Perfluoroalkyl group of (1), substituted or unsubstituted C6-C20Or substituted or unsubstituted C6-C20The heteroaryl group of (a);
X1、X1a、X1b、X1c、X1dand X1eIndependently is halogen or C1-C8Alkoxy group of (a);
wherein, said substituted C6-C20Aryl of (a) or said substituted C2-C20Said substitution in heteroaryl means substitution with one or more of the following substituents: halogen (the halogen is preferably F, Cl, Br or I), C1-C16Hydrocarbyloxy group of (said C)1-C16The hydrocarbyloxy group of (A) is preferably C1-C8Hydrocarbyloxy groups of (a); said C1-C8The hydrocarbyloxy group of (A) is preferably C1-C4Hydrocarbyloxy groups of (a); said C1-C4The hydrocarbyloxy group of (A) is preferably methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy or tert-butoxy), C1-C16Alkyl (said C)1-C16The alkyl group of (A) is preferably C1-C8Alkyl groups of (a); said C1-C8The alkyl group of (A) is preferably C1-C4Alkyl groups of (a); said C1-C4The alkyl group of (A) is preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl), C1-C16Fluoroalkyl (meth)C is1-C16By fluoroalkyl is meant C substituted by one or more fluorine atoms1-C16Alkyl groups of (a); said C1-C16The fluoroalkyl group of (A) is preferably C1-C8A fluoroalkyl group of (a); said C1-C8The fluoroalkyl group of (A) is preferably C1-C4A fluoroalkyl group of (a); said C1-C4The fluoroalkyl group of (a) is preferably a trifluoromethyl group), a nitro group or an amino group, and when the substituent is plural, the substituents are the same or different.
R1、R1a、R1b、R1c、R1d、R1e、R2、R2’、R2a、R2a’、R2b、R2b’、R2c、R2c’、Ra、Rb、R4、R4a、R4b、Rc、Rc’、Rc"and R5In (b), the C1-C8The alkyl group of (A) is preferably C1-C4Alkyl of (a), said C1-C4The alkyl group of (a) is preferably a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group or a tert-butyl group.
R1、R1a、R1b、R1c、R1d、R1e、R2、R2’、R2a、R2a’、R2b、R2b’、R2c、R2c’And R5In (b), the C3-C6The cycloalkyl group of (b) is preferably cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
R1、、R1a、R1b、R1c、R1d、R1e、R2、R2’、R2a、R2a’、R2b、R2b’、R2c、R2c’、Ra、RbAnd R5In (b), the C1-C8Is preferably perfluoroalkylIs composed of Wherein, including the respective isomeric forms.
R1、R1a、R1b、R1c、R1d、R1e、R2、R2’、R2a、R2a’、R2b、R2b’、R2c、R2c’、Ra、RbAnd R5Wherein said substituted or unsubstituted C6-C20Aryl of (A) is preferably substituted or unsubstituted C6-C14Aryl group of (1). Said substituted or unsubstituted C6-C14The aryl group of (A) is preferably a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted 9-anthracenyl groupOr substituted or unsubstituted 9-phenanthrylSaid substituted phenyl is preferably
R1、R1a、R1b、R1c、R1d、R1e、R2、R2’、R2a、R2a’、R2b、R2b’、R2c、R2c’、Ra、RbAnd R5Wherein said substituted or unsubstituted C2-C20The heteroaryl group of (A) preferably means a substituted or unsubstituted C having O, N or S as a heteroatom and 1 to 4 heteroatoms2-C20The heteroaryl group of (a). The heteroatom is O, N or S, and the heteroatom number is 1-4 substituted or unsubstituted C2-C20The heteroaryl group of (A) is preferably substituted or unsubstituted C2-C10The heteroaryl group of (a). Said substituted or unsubstituted C2-C10The heteroaryl group of (a) is preferably a substituted or unsubstituted furyl group, a substituted or unsubstituted pyridyl group, or a substituted or unsubstituted thienyl group.
Rb、X1、X1a、X1b、X1c、X1dAnd X1eIn (b), the C1-C8Alkoxy of (3) is preferably C1-C4Alkoxy group of (2). Said C1-C4The alkoxy group of (b) is preferably methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy or tert-butoxy.
X1、X1a、X1b、X1c、X1dAnd X1eThe halogen is preferably fluorine, chlorine, bromine or iodine.
When R is2And R2’And the carbon atoms to which they are attached together form C5-C8In the case of a cycloalkyl group of (A), said C5-C8The cycloalkyl group of (b) is preferably cyclopentyl or cyclohexyl.
R3In (1), thePreferably is
R3In (1), thePreferably is
R4、R4aOr R4bIn (1), thePreferably is
Preferably, the first and second liquid crystal films are made of a polymer,
in the general formula I, R1Is C3-C6Cycloalkyl or substituted or unsubstituted C6-C20Aryl of (a); x1Is halogen or C1-C8Alkoxy group of (2). In the general formula IThe structures may also contain chiral centres, e.g.
In the general formula II, R1aIs C3-C6Cycloalkyl or substituted or unsubstituted C6-C20Aryl of (a); r2And R2’Independently is substituted or unsubstituted C6-C20Or substituted or unsubstituted C2-C20The heteroaryl group of (a); or R2And R2’And the carbon atoms to which they are attached together form C5-C8Cycloalkyl groups of (a); r3Is composed ofWherein R isaIs C1-C8Alkyl of (C)1-C8Perfluoroalkyl group of (1), substituted or unsubstituted C6-C20Aryl of (2), or substituted or unsubstituted C2-C20The heteroaryl group of (a); rbIs C1-C8Alkyl of (C)1-C8Alkoxy group of (C)1-C8Perfluoroalkyl group of (1), substituted or unsubstituted C6-C20Aryl of (2), or substituted or unsubstituted C2-C20The heteroaryl group of (a); x1aIs halogen or C1-C8Alkoxy group of (a);
in the general formula III, R1bIs substituted or unsubstituted C6-C20Aryl of (a); r2a、R2a’And R4Independently is C1-C8Alkyl groups of (a); x1bIs halogen;
in the general formula IV, R1cIs substituted or unsubstituted C6-C20Aryl of (a); r2bAnd R2b’Independently is C1-C8Alkyl of (C)1-C8Perfluoroalkyl group of (1), substituted or unsubstituted C6-C20Or substituted or unsubstituted C2-C20The heteroaryl group of (a); r4aIndependently of one another is hydrogen, C1-C8Alkyl orWherein R isc、Rc' or Rc"independently is C1-C8Alkyl groups of (a); r5Is hydrogen or halogen; x1cIs halogen or C1-C8Alkoxy group of (a);
in the general formula V, R1dIs substituted or unsubstituted C6-C20Aryl of (a); r2c、R2c’And R4bIndependently of one another is hydrogen, C1-C8Alkyl of (C)1-C8Perfluoroalkyl group of (1), substituted or unsubstituted C6-C20Or substituted or unsubstituted C2-C20The heteroaryl group of (a); x1cIs halogen or C1-C8Alkoxy group of (a);
in the general formula VI, R1eIs substituted or unsubstituted C6-C20Aryl of (a); x1eIs halogen or C1-C8Alkoxy group of (2).
The compound shown in the general formula I is preferably any one of the following compounds:
the compound represented by the formula II is preferably any one of the following compounds:
the compound represented by the formula III is preferably any one of the following compounds:
the compound represented by the formula IV is preferably any one of the following compounds:
the compound represented by the formula V is preferably any one of the following compounds:
the compound represented by formula VI is preferably any of the following compounds:
the invention also provides a single crystal of the metal iridium complex IIIa, which belongs to a monoclinic system in a single crystal X-ray diffraction spectrum using a radiation source Cu-K α, has a space group of P21, and has the following unit cell parameters: α -90 °, β -92.5300 (10 °), γ -90 °, unit cell volumeThe number of asymmetric units in the unit cell, Z, is 2;
the invention also provides a preparation method of the single crystal of the metal-iridium complex IIIa, which comprises the following steps: and (3) mixing the metal iridium complex IIIa and a benign solvent, then dropwise adding the poor solvent until turbidity just appears, dropwise adding the benign solvent, and standing.
The benign solvent is preferably a solvent having good solubility for the metal complex IIIa (solubility greater than 0.1mg/10mL at room temperature under 1 atm), and preferably a halogenated hydrocarbon solvent. The halogenated hydrocarbon solvent is preferably Dichloromethane (DCM). The amount of the benign solvent to be used is not particularly limited as long as the metal complex IIIa can be dissolved to give a clear and transparent solution. In general, the ratio of the benign solvent to the metal complex IIIa is preferably from 1mL/20mg to 1mL/40mg by volume.
The poor solvent is preferably a solvent having poor solubility (solubility of less than 0.1mg/100mL at room temperature under 1 standard atmosphere) for the metal-containing complex IIIa, and is preferably an alkane solvent. The alkane solvent is preferably n-hexane. The amount of the poor solvent is not particularly limited, and is generally such that the poor solvent is added dropwise to a solution of the iridium complex IIIa and the benign solvent just before clouding occurs. The volume and mass ratio of the poor solvent to the metal iridium complex IIIa is preferably 1mL/5mg-1mL/1 mg.
The mixing temperature may be a temperature conventional in the art, and is preferably 10 to 30 ℃. The temperature of said standing may be a temperature conventional in the art, preferably from-30 ℃ to-50 ℃.
The invention also provides a preparation method of the metal iridium complex shown in the general formula I, the general formula II, the general formula III, the general formula IV, the general formula V or the general formula VI, which comprises the following steps: in an organic solvent, in the presence of alkali, a compound shown as a formula a and [ Ir (cod) X1]2A compound represented by the formula b and [ Ir (cod) X1a]2A compound represented by the formula c and [ Ir (cod) X1b]2A compound represented by the formula d and [ Ir (cod) X1c]2A compound represented by the formula e and [ Ir (cod) X1d]2Or a compound of formula f with [ Ir (cod) X1e]2Carrying out a complexation reaction as shown below; respectively preparing metal iridium complexes shown in a general formula I, a general formula II, a general formula III, a general formula IV, a general formula V or a general formula VI;
wherein, the symbols, the radicalsThe definitions are all as described above; y is halogen, CF3SO3、OTf、BF4Or ClO4。
In Y, the halogen is preferably fluorine, chlorine, bromine or iodine. [ Ir (cod) X1]2～[Ir(cod)X1e]2In the above formula, cod means 1, 5-cyclooctadiene.
The methods and conditions of the complexation reaction may be those conventional in the art. The following methods are preferred in the present invention: the organic solvent is preferably one or more of aromatic hydrocarbon solvents, halogenated hydrocarbon solvents, ether solvents, amide solvents, alkane solvents and nitrile solvents, and more preferably ether solvents. The aromatic hydrocarbon solvent is preferably one or more of benzene, toluene and xylene. The halogenated hydrocarbon solvent is preferably carbon tetrachloride (CCl)4) Dichloromethane (DCM) and trichloromethane (CHCl)3) One or more of (a). The ethereal solvent is preferably one or more of Tetrahydrofuran (THF), diethyl ether and 1, 4-dioxane, more preferably tetrahydrofuran. The amide solvent is preferably N, N-Dimethylformamide (DMF). The alkane solvent is preferably one or more of cyclohexane, n-pentane, n-hexane and n-heptane. The nitrile solvent is preferably acetonitrile. The base may be any base conventional in the art, preferably an inorganic base and/or an organic base. The inorganic base may be an inorganic base conventional in this kind of reaction in the art, and preferably is one or more of sodium carbonate, potassium carbonate, cesium carbonate, potassium phosphate, sodium hydride, sodium methoxide, sodium ethoxide, sodium acetate, potassium tert-butoxide, sodium tert-butoxide, and lithium tert-butoxide. The organic base may be an organic base conventional in the art for such reactions, preferably one or more of triethylamine, piperidine, pyridine, N-lutidine and 2, 6-lutidine. The [ Ir (cod) X1]2And a compound shown as a formula [ Ir (cod) X1a]2And a compound represented by the formula b, [ Ir (cod) X1b]2And a compound represented by the formula c, [ Ir (cod) X1c]2And a compound represented by the formula d, [ Ir (cod) X1d]2And a compound represented by the formula e or [ Ir (cod) X1e]2The molar ratio to the compound represented by the formula f is preferably 1:1 to 1:3.5, more preferably 1:2 to 1: 3.5. The [ Ir (cod) X1]2、[Ir(cod)X1a]2、[Ir(cod)X1b]2、[Ir(cod)X1c]2、[Ir(cod)X1d]2Or [ Ir (cod) X1e]2The molar ratio to the base is preferably from 1:1 to 1:20, more preferably from 2:15 to 1: 20. The organic solvent is mixed with [ Ir (cod) X1]2、[Ir(cod)X1a]2、[Ir(cod)X1b]2、[Ir(cod)X1c]2、[Ir(cod)X1d]2Or [ Ir (cod) X1e]2The volume/mass ratio of (B) is preferably 0.1mL/mg to 1 mL/mg. The reaction temperature is preferably from 0 ℃ to 150 ℃, more preferably from 25 ℃ to 125 ℃. The time for the complexing reaction is preferably 20 to 48 hours.
After the reaction is finished, the method can also comprise the operation of post-treatment. The post-treatment method can be a conventional method for post-treatment in the field, and preferably comprises the steps of removing the solvent from the reaction solution after the reaction is finished, and separating and purifying the crude product by recrystallization, thin-layer chromatography or column chromatography. The recrystallization solvent, the thin-layer chromatography developer, or the eluent for column chromatography is preferably a mixture of a polar solvent and a nonpolar solvent. The polar solvent is preferably an alcohol solvent and/or an ester solvent. The alcohol solvent is preferably one or more of methanol, ethanol and isopropanol. The ester solvent is preferably ethyl acetate. The nonpolar solvent is preferably a chlorinated hydrocarbon solvent and/or an alkane solvent. The chlorinated hydrocarbon solvent is preferably dichloromethane. The alkane solvent is preferably petroleum ether and/or n-hexane. The solvent for recrystallization is preferably one or more of dichloromethane-n-hexane, isopropanol-petroleum ether, ethyl acetate-n-hexane, and isopropanol-ethyl acetate-petroleum ether. The developing solvent for thin layer chromatography or the eluent for column chromatography is preferably one or more of isopropanol-petroleum ether, isopropanol-dichloromethane, methanol-dichloromethane, ethyl acetate-petroleum ether, ethyl acetate-n-hexane, and isopropanol-ethyl acetate-petroleum ether. In the recrystallization solvent, the thin-layer chromatography developer, or the eluent of column chromatography, the volume ratio of the polar solvent to the nonpolar solvent is preferably 1:1 to 1: 500. For example: ethyl acetate: petroleum ether ═ 1:1 to 1:500, and isopropanol: petroleum ether is 1:1 to 1: 500.
The invention also provides application of the metal iridium complex shown in the general formula I, the general formula II, the general formula III, the general formula IV, the general formula V or the general formula VI as a catalyst in asymmetric allyl substitution reaction.
The asymmetric allylic substitution reaction preferably comprises the steps of: in an organic solvent, under the action of alkali, and under the catalysis of one or more of the metal iridium complexes shown in the general formula I, the general formula II, the general formula III, the general formula IV, the general formula V or the general formula VI, carrying out asymmetric allyl substitution reaction shown in the following formula S1 on the compound shown in the formula S1 to obtain a benzindole compound shown in the formula P; wherein, the carbon marked by the letter is chiral carbon or non-chiral carbon, and when the carbon is chiral carbon, the chiral carbon is in S configuration or R configuration;
in the compound shown as the formula S1 and the compound shown as the formula P, Ra1Is mono-or polysubstituted, the same or different, selected from one or more of the following substituents: halogen, substituted or unsubstituted C1-C4Or substituted or unsubstituted C1-C4Alkoxy group of (a); rb1Is substituted or unsubstituted C1-C4Or substituted or unsubstituted C2-C4Alkenyl of (a); rc1Is composed ofWherein M is O or NH; rd1Is C1-C4Alkyl, C substituted by one or more halogens1-C4Alkyl or C1-C4Alkoxy group of (a); re1Is C1-C4Alkyl or C6-C20An aryl group; ra1And Rb1In (b), said substituted C1-C4Alkyl of (2) or said substituted C1-C4The substituent in the alkoxy group of (a) means a substituent substituted with one or more of the following substituents: halogen (the halogen is F, Cl, Br or I), C1-C4Alkoxy of (said C)1-C4The alkoxy group of (B) is preferably methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy or tert-butoxy), C1-C4Alkyl (said C)1-C4The alkyl group of (A) is preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl), C6～C20Aryl (said C)6～C20Aryl is preferably phenyl, or substituted by one or more C1-C4Alkoxy-substituted C6-C20Aryl, when there are more than one substituent, said substituents may be the same or different (said being substituted by one or more C's)1-C4Alkoxy-substituted C6-C20Aryl is preferably p-methoxyphenyl), and when the substituent is plural, the substituents may be the same or different.
Ra1In (3), the halogen is preferably F, Cl, Br or I.
Ra1Or Rb1Wherein said substituted or unsubstituted C1-C4The alkyl group of (a) is preferably a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted n-propyl group, a substituted or unsubstituted isopropyl group, a substituted or unsubstituted n-butyl group, a substituted or unsubstituted isobutyl group, or a substituted or unsubstituted tert-butyl group. The substituted methyl group is preferably benzyl or p-methoxybenzyl.
Ra1Wherein said substituted or unsubstituted C1-C4The alkoxy group of (b) is preferably a substituted or unsubstituted methoxy group, a substituted or unsubstituted ethoxy group, a substituted or unsubstituted n-propoxy group, a substituted or unsubstituted isopropoxy group, a substituted or unsubstituted n-butoxy group, a substituted or unsubstituted isobutoxy group, or a substituted or unsubstituted tert-butoxy group.
Rb1In (b), the C2-C4The alkenyl group of (A) is preferably an ethenyl group, a 1-propenyl group, a 2-propenyl group, a 1-butenyl group, a 2-butenyl group or a 3-butenyl group.
Rd1Or Re1In (b), the C1-C4The alkyl group of (a) is preferably a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group or a tert-butyl group.
Rd1In (b), the C1-C4The alkoxy group of (b) is preferably methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy or tert-butoxy.
Rd1Wherein said C is substituted by one or more halogens1-C4Said halogen in the alkyl group of (a) preferably means fluorine, chlorine, bromine or iodine; said C substituted by one or more halogens1-C4C in the alkyl group of (1)1-C4The alkyl group of (a) is preferably a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group or a tert-butyl group. Said C substituted by one or more halogens1-C4The alkyl group of (A) is preferably
Re1In (b), the C6-C20Aryl is preferably phenyl.
The asymmetric allylic substitution reaction may be conventional in the art for such reactions, preferably, only in the general formula I, formula IIIII, formula IV, formula V or formula VI, without further catalyst, such as a copper-based catalyst and/or a palladium-based catalyst. The asymmetric allylic substitution reaction is preferably carried out under gas protection. The gas is preferably an inert gas, such as argon. The organic solvent may be an organic solvent that is conventional in the art, as long as the reaction is not affected, and in the present invention, one or more of an aromatic hydrocarbon solvent, a halogenated hydrocarbon solvent, an ether solvent, an amide solvent, an alkane solvent, and a nitrile solvent are preferred. The aromatic hydrocarbon solvent is preferably toluene. The halogenated hydrocarbon solvent is preferably Dichloromethane (DCM) and/or trichloromethane (CHCl)3). The ethereal solvent is preferably one or more of Tetrahydrofuran (THF), diethyl ether and 1, 4-dioxane. The alkane solvent is preferably n-hexane. The nitrile solvent is preferably acetonitrile. The base is preferably an organic base and/or an inorganic base. The organic base may be any organic base conventional in the art, preferably 1, 8-diazabicycloundecen-7-ene (DBU), N-Diisopropylethylamine (DIEA), triethylamine (Et)3N) and 1, 4-diazabicyclo [2.2.2]One or more of octane (DABCO). The inorganic base may be any conventional inorganic base in the art, preferably Cs2CO3、K2CO3、Na2CO3、Li2CO3Lithium tert-butoxide (c)tBuoli), sodium tert-butoxide (tBuona) and potassium tert-butoxide (tBuOK). The molar ratio of the metal iridium complex to the compound shown as the formula S1 can be selected according to the conventional molar ratio of the conventional reaction in the field, and is preferably 0.01: 1-0.1: 1. The molar ratio of the base to the compound of formula S1 may be conventional in the art, and is preferably 0.1:1 to 1: 1. The dosage of the solvent does not influence the reaction, and preferably, the volume-mass ratio of the solvent to the compound shown in the formula A is 10mL/g-100 mL/g. The reaction temperature is preferably 0 to 120 ℃, more preferably 25 to 85 ℃. The progress of the reaction can be achieved by the methods known in the artThe reaction is generally terminated when the compound of formula S1 disappears, and the reaction time is preferably 2 to 48 hours.
The invention also provides a benzindole compound shown as the formula P, wherein carbon marked by x is chiral carbon or non-chiral carbon, and when the carbon is chiral carbon, the chiral carbon is S configuration or R configuration;
wherein R isa1And Rb1The definitions of (A) and (B) are the same as described above; however, the compounds of formula P do not include compounds of any of the following structures:
the compound shown in the formula P is preferably any one of the following compounds:
the above preferred conditions can be arbitrarily combined to obtain preferred embodiments of the present invention without departing from the common general knowledge in the art.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows:
(1) the metal iridium complex containing the chiral triazole carbene is stable in air and convenient to store. The metal iridium complex can be subjected to column chromatography purification, recrystallization and other operations in the air, and has no influence on products. The metal iridium complex is placed in the air for six months, the purity (97 percent) of the metal iridium complex is not changed, when the metal iridium complex is used as a catalyst for catalyzing allyl substitution reaction, the yield and the purity of a target compound are not influenced, and the catalytic effect is the same as that of the new preparation.
(2) The preparation method of the metal iridium complex has the advantages of mild reaction conditions, simple operation, easily obtained raw materials, high yield and simple post-treatment.
(3) The metal iridium complex containing the chiral triazole carbene can be applied to various different types of asymmetric intermolecular allyl substitution reactions and intramolecular substitution reactions catalyzed by metal iridium, achieves high yield, high regioselectivity and high enantioselectivity, can be applied to more complex substrate reactions, and greatly expands the application range of the asymmetric intermolecular allyl substitution reactions and the intramolecular substitution reactions.
Drawings
FIG. 1 is a single crystal structural view of a compound IIIa obtained in example 3.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
Wherein compounds a, b, c, d, e and f can be prepared according to methods conventional in the art, see in particular (a) chem.commu.2008, 2263.(b) j.org.chem.2005,70,5725.(c) org.biomol.chem.2011,9,2072.(d) org.lett.2008,10,277.(e) angelw.chem.int.ed.2002, 41,1743.(f) j.am.chem.soc.2007,129,10098.
Example 1 Synthesis of a Metal Iridium Complex represented by the general formula I
Under the protection of argon, a dry 250 ml three-neck bottle is added with [ Ir (cod) Cl]2(336mg,0.5mmol) of a compound represented by the formula a and a base, adding an organic solvent, stirring for reaction for 24 hours, and separating the crude product by column chromatography (ethyl acetate/petroleum ether ═ 1: 5). Specific reaction conditions for compounds Ia-Ic and compound If are shown in Table 1. The preparation methods and conditions of the compounds Id-Ie and Ig-Ik are described in example 1 and Table 1, wherein the molar ratio in Table 1 is [ Ir (cod) X1]2: a compound a: molar ratio of the base.
TABLE 1
Compound Ia
Yellow solid, yield: 54% (> 97% purity, nuclear magnetic purity)
1H NMR(300MHz,CDCl3)δ8.32(d,J＝7.2Hz,2H),7.49-7.46(m,3H),4.94(AB,JAB＝15.0Hz,1H),4.80-4.71(m,3H),4.44-4.38(m,2H),3.89(d,J＝6.9Hz,1H),2.85-2.78(m,1H),2.36-1.67(m,8H),1.51-1.22(m,5H),1.06(s,3H),0.95(s,3H),0.88(s,3H).
13C NMR(100MHz,CDCl3)δ181.5,149.3,140.2,128.44,128.38,128.2,124.4,123.9,85.1,84.6,61.4,59.4,54.5,52.0,50.1,47.6,33.2,32.51,32.49,29.9,28.5,25.4,22.0,21.2,11.4.
Elemental analysis: calcd for C27H35N3ClOIr is C, 50.26; h, 5.47; n,6.51 Experimental value (Found): C,50.26；H,5.43；N,6.38.
Compound Ib
Yellow solid, yield: 44% (> 97% purity, nuclear magnetic purity)
1H NMR(300MHz,CDCl3)δ7.03(s,1H),6.90(s,1H),4.90(AB,JAB＝14.7Hz,1H),4.62-4.53(m,4H),4.41(AB,JAB＝14.7Hz,1H),3.95(d,J＝6.9Hz,1H),3.05(d,J＝8.4Hz,1H),2.67-2.63(m,1H),2.37(s,3H),2.36(s,3H),2.10-1.89(m,4H),1.84(s,3H),1.71-1.26(m,7H),1.09(d,J＝6.0Hz,1H),1.05(s,3H),0.95(s,3H),0.82(s,3H).
13C NMR(75MHz,CDCl3)δ181.5,148.6,139.3,136.5,136.2,135.4,129.2,128.1,84.8,84.1,84.0,61.0,59.2,53.2,51.5,51.1,50.2,47.7,33.6,33.1,32.7,29.1,29.0,25.1,21.9,21.2,20.6,19.5,17.5,11.4.
Elemental analysis: calcd for C30H41N3ClOIr is C, 52.42; h, 6.01; n,6.11 Experimental values (Found) C, 52.62; h, 6.03; and N,6.04.
Compound Ic
Yellow solid, yield: 40% (> 97% purity, nuclear magnetic purity)
1H NMR(400MHz,CD2Cl2)δ9.43(s,2H),7.94(s,1H),5.01(AB,JAB＝13.6Hz,1H),4.95-4.91(m,1H),4.76-4.71(m,1H),4.57(d,J＝4.4Hz,1H),4.43(AB,JAB＝15.2Hz,1H),4.03-3.98(m,2H),2.85-2.80(m,1H),2.54(t,J＝7.2Hz,1H),2.35-2.27(m,1H),2.13-1.99(m,4H),1.87-1.81(m,1H),1.71(dt,J＝2.8,12.0Hz,1H),1.58-1.55(m,2H),1.51-1.47(m,1H),1.39-1.33(m,1H),1.30-1.26(m,1H),1.04(s,3H),0.90(s,3H),0.87(s,3H).
13C NMR(100MHz,CD2Cl2)δ186.3,149.9,141.5,131.8(q,J＝33.4Hz),124.9(m),123.9,121.4(m),87.6,87.1,85.4,62.7,59.6,55.0,52.3,51.2,50.2,48.7,34.5,33.0,32.4,31.0,28.1,26.9,21.6,20.6,11.3.
19F NMR(376MHz,CD2Cl2)δ-63.1(s).
Elemental analysis: calcd for C29H33N3F6ClOIr is C, 44.58; h, 4.26; n,5.38, Experimental value (Found) C, 44.45; h, 4.34; and N,5.12.
Compound Id
Yellow solid, yield: 57% (> 97% purity, nuclear magnetic purity)
1H NMR(400MHz,DMSO-d6)δ8.57(d,J＝8.0Hz,1H),7.36(d,J＝7.6Hz,1H),7.30(t,J＝7.6Hz,1H),7.17(t,J＝7.2Hz,1H),6.02(d,J＝3.2Hz,1H),5.00(AB,JAB＝15.6Hz,1H),4.94(t,J＝3.6Hz,1H),4.91(AB,JAB＝16.0Hz,1H),4.60-4.56(m,1H),4.38-4.35(m,1H),3.46-3.41(m,2H),3.30-3.27(m,1H),3.04(AB,JAB＝16.8Hz,1H)2.13-2.09(m,1H),2.00-1.88(m,3H),1.71-1.58(m,4H).
13C NMR(100MHz,DMSO-d6)δ187.8,149.9,140.8,138.5,128.6,126.6,126.5,125.0,87.8,86.2,78.2,62.0,59.7,54.5,52.9,36.9,33.4,33.0,28.9,28.7,27.6.
19F NMR(376MHz,DMSO-d6)δ-138.6(d,J＝23.3Hz),-144.6(d,J＝24.8Hz),-150.3(t,J＝22.6Hz),-161.9(t,J＝23.7Hz),-162.6(t,J＝23.3Hz).
Elemental analysis: calcd for C26H22N3F5ClOIr is C, 43.67; h, 3.10; n,5.88 Experimental values (Found) C, 43.62; h, 3.02; n,5.71.
Compound Ie
Yellow solid, yield: 50% (> 97% purity, nuclear magnetic purity)
1H NMR(300MHz,CDCl3)δ8.32(d,J＝7.2Hz,2H),7.49-7.46(m,3H),4.94(AB,JAB＝15.0Hz,1H),4.80-4.71(m,3H),4.44-4.38(m,2H),3.89(d,J＝6.9Hz,1H),3.62(s,3H),2.85-2.78(m,1H),2.36-1.67(m,7H),1.51-1.22(m,5H),1.06(s,3H),0.95(s,3H),0.88(s,3H).
13C NMR(100MHz,CDCl3)δ181.5,149.3,140.2,128.44,128.38,128.2,124.4,123.9,85.1,84.6,61.4,59.4,54.5,52.0,50.1,47.6,33.2,32.51,32.49,29.9,28.5,25.4,22.0,21.2,11.4.
MS(ESI+):675(C28H37ClIrN3O2[M+]).
Compound If
Yellow solid, yield: 60% (> 97% purity, nuclear magnetic purity)
1H NMR(300MHz,CDCl3)δ8.32(d,J＝7.2Hz,2H),7.49-7.46(m,3H),4.94(AB,JAB＝15.0Hz,1H),4.80-4.71(m,3H),4.44-4.38(m,2H),3.89(d,J＝6.9Hz,1H),3.51(s,3H),2.85-2.78(m,1H),2.36-1.67(m,8H),1.51-1.22(m,5H),1.06(s,3H),0.95(s,3H),0.88(s,3H).
13C NMR(100MHz,CDCl3)δ181.5,149.3,140.2,128.44,128.38,128.2,124.4,123.9,85.1,84.6,61.4,59.4,54.5,52.0,50.1,47.6,33.2,32.51,32.49,29.9,28.5,25.4,22.0,21.2,11.4.
MS(ESI+):641(C28H38IrN3O2[M+]).
Compound Ig
Yellow solid, yield: 55% (> 97% purity, nuclear magnetic purity)
MS(ESI+):745(C35H39IrN3O[M+]).
Compound Ih
Yellow solid, yield: 57% (> 97% purity, nuclear magnetic purity)
MS(ESI+):745(C35H39IrN3O[M+]).
Compound Ii
Yellow solid, yield: 52% (> 97% purity, nuclear magnetic purity)
MS(ESI+):651(C27H4139IrN3O[M+]).
Compound Ij
Yellow solid, yield: 50% (> 97% purity, nuclear magnetic purity)
MS(ESI+):659(C28H4137IrN3O[M+]).
Compound Ik
Yellow solid, yield: 55% (> 97% purity, nuclear magnetic purity)
MS(ESI+):690(C27H4134ClIrN4O3[M+]).
Example 2 Synthesis of Metal Iridium Complex represented by general formula II
Adding [ Ir (cod) X into a dry 250 ml three-mouth bottle under the protection of argon1a]2(336mg,0.5mmol), the compound represented by the formula b, a base and an organic solvent, stirring for reaction, and separating the crude product by column chromatography (ethyl acetate/petroleum ether: 1: 5). Specific reaction conditions for compounds IIa-IIc and IIf are shown in Table 2. The preparation methods and conditions of the compounds IId to IIe, IIg to IIu are described in reference to example 2 and Table 2, wherein the molar ratios in Table 2 refer to [ Ir (cod) X1a]2: compound b: molar ratio of the base.
TABLE 2
Compound IIa
Yellow solid, yield: 55% (> 97% purity, nuclear magnetic purity)
MS(ESI+):858(C39H42ClIrN4O2S[M+]).
Compound IIb
Yellow solid, yield: 56% (> 97% purity, nuclear magnetic purity)
MS(ESI+):900(C42H48ClIrN4O2S[M+]).
Compound IIc
Yellow solid, yield: 52% (> 97% purity, nuclear magnetic purity)
MS(ESI+):994(C41H40ClF6IrN4O2S[M+]).
Compound IId
Yellow solid, yield: 52% (> 97% purity, nuclear magnetic purity)
MS(ESI+):948(C39H37ClF5IrN4O2S[M+]).
Compound IIe
Yellow solid, yield: 53% (> 97% purity, nuclear magnetic purity)
MS(ESI+):888(C32H32ClIrN4O3S[M+]).
Compound IIf
Yellow solid, yield: 53% (> 97% purity, nuclear magnetic purity)
MS(ESI+):854(C32H32ClIrN4O3S[M+]).
Compound IIg
Yellow solid, yield: 56% (> 97% purity, nuclear magnetic purity)
MS(ESI+):974(C48H50ClIrN4O2S[M+]).
Compound IIh
Yellow solid, yield: 53% (> 97% purity, nuclear magnetic purity)
MS(ESI+):974(C48H50ClIrN4O2S[M+]).
Compound IIi
Yellow solid, yield: 53% (> 97% purity, nuclear magnetic purity)
MS(ESI+):888(C41H48ClIrN4O2S[M+]).
Compound IIj
Yellow solid, yield: 55% (> 97% purity, nuclear magnetic purity)
MS(ESI+):880(C40H52ClIrN4O2S[M+]).
Compound IIk
Yellow solid, yield: 53% (> 97% purity, nuclear magnetic purity)
MS(ESI+):919(C40H45ClIrN5O4S[M+]).
Compound IIl
Yellow solid, yield: 59% (> 97% purity, nuclear magnetic purity)
MS(ESI+):776(C32H44ClIrN4O2S[M+]).
Compound IIm
Yellow solid, yield: 50% (> 97% purity, nuclear magnetic purity)
MS(ESI+):762(C35H42ClIrN4O[M+]).
Compound IIn
Yellow solid, yield: 50% (> 97% purity, nuclear magnetic purity)
MS(ESI+):792(C36H44ClIrN4O2[M+]).
Compound IIo
Yellow solid, yield: 52% (> 97% purity, nuclear magnetic purity)
MS(ESI+):898(C37H40ClF6IrN4O[M+]).
Compound IIp
Yellow solid, yield: 60% (> 97% purity, nuclear magnetic purity)
MS(ESI+):804(C38H48ClIrN4O[M+]).
Compound IIq
Yellow solid, yield: 54% (> 97% purity, nuclear magnetic purity)
MS(ESI+):862(C41H54ClIrN4O2[M+]).
Compound IIr
Yellow solid, yield: 54% (> 97% purity, nuclear magnetic purity)
MS(ESI+):858(C38H45ClF3IrN4O[M+]).
Compound IIs
Yellow solid, yield: 55% (> 97% purity data, nuclear magnetic purity)
MS(ESI+):894(C37H45ClF3IrN4O2S[M+]).
Compound IIt
Yellow solid, yield: 50% (> 97% purity, nuclear magnetic purity)
MS(ESI+):1244(C44H45ClF17IrN4O2S[M+]).
Example 3 Synthesis of a Metal Iridium Complex represented by the formula III
Adding [ Ir (cod) X into a dry 250 ml three-mouth bottle under the protection of argon1b]2(336mg,0.5mmol) of the compound represented by the formula c, a base and an organic solvent, and stirring to react. The crude product is isolated by column chromatography (ethyl acetate/petroleum ether: 1: 5). See Table 3 for specific reaction conditions for compounds IIIa-IIIc and IIIf. The preparation methods and conditions of the compounds IIId to IIIe refer to example 3 and Table 3, wherein the molar ratio in Table 3 means [ Ir (cod) X1b]2: compound c: molar ratio of the base.
TABLE 3
MS(ESI+):1244(C44H45ClF17IrN4O2S[M+]).
Compound IIIa
Yellow solid, yield: 61% (> 97% purity, nuclear magnetic purity)
MS(ESI+):579(C22H29ClIrN3O[M+]).
The preparation method of the compound IIIa single crystal comprises the following steps: dissolve 100mg of Compound IIIa in 5mL CH2Cl2Then n-hexane (2mL) was added dropwise thereto until just turbidity appeared. Adding a drop of CH thereto2Cl2The resulting precipitate was dissolved again. The solution was left to stand in a refrigerator at-30 ℃ until the compound IIIa single crystal was formed.
Crystal data in a single crystal X-ray diffraction spectrum using a radiation source of Cu-K α, the crystal is monoclinic, space group is P21, and unit cell parameters are:α＝90°
β＝92.5300(10)°
γ＝90°
cell volumeThe number of asymmetric units in the unit cell, Z, is 2.
Compound IIIb
Yellow solid, yield: 63% (> 97% purity, nuclear magnetic purity)
MS(ESI+):621(C25H35ClIrN3O[M+]).
Compound IIIc
Yellow solid, yield: 60% (> 97% purity, nuclear magnetic purity)
MS(ESI+):715(C24H27ClF6IrN3O[M+]).
Compound IIId
Yellow solid, yield: 60% (> 97% purity, nuclear magnetic purity)
MS(ESI+):609(C23H31ClF6IrN3O2[M+]).
Compound IIIe
Yellow solid, yield: 62% (> 97% purity, nuclear magnetic purity)
MS(ESI+):669(C22H24ClF5IrN3O[M+]).
Compound IIIf
Yellow solid, yield: 62% (> 97% purity, nuclear magnetic purity)
MS(ESI+):665(C23H27F5IrN3O[M+]).
Example 4 Synthesis of Metal Iridium Complex represented by general formula IV
Adding [ Ir (cod) X into a dry 250 ml three-mouth bottle under the protection of argon1c]2(336mg,0.5mmol), a compound represented by the formula d, a base and an organic solvent, stirring for reaction, and separating the crude product by column chromatography (ethyl acetate/petroleum ether: 1: 5). See table 4 for specific reaction conditions for compounds IVa-IVc and compound IVf. The preparation methods and conditions of the compounds IVd-IVe, IVg-IVi refer to example 4 and Table 4, wherein the molar ratio in Table 4 refers to [ Ir (cod) X1c]2: a compound d: molar ratio of the base.
TABLE 4
Compound VIa
Yellow solid, yield: 53% (> 97% purity, nuclear magnetic purity)
MS(ESI+):821(C38H51ClIrN3OSi[M+]).
Compound VIb
Yellow solid, yield: 57% (> 97% purity, nuclear magnetic purity)
MS(ESI+):863(C41H57ClIrN3OSi[M+]).
Compound VIc
Yellow solid, yield: 59% (> 97% purity, nuclear magnetic purity)
MS(ESI+):957(C40H49ClF6IrN3OSi[M+]).
Compound VId
Yellow solid, yield: 59% (> 97% purity, nuclear magnetic purity)
MS(ESI+):851(C39H53ClIrN3O2Si[M+]).
Compound VIe
Yellow solid, yield: 59% (> 97% purity, nuclear magnetic purity)
MS(ESI+):911(C38H46ClF5IrN3OSi[M+]).
Compound VIf
Yellow solid, yield: 53% (> 97% purity, nuclear magnetic purity)
MS(ESI+):817(C39H54ClIrN3O2Si[M+]).
Compound VIg
Yellow solid, yield: 53% (> 97% purity, nuclear magnetic purity)
MS(ESI+):859(C42H60ClIrN3O2Si[M+]).
Compound VIh
Yellow solid, yield: 53% (> 97% purity, nuclear magnetic purity)
MS(ESI+):641(C26H40ClFIrN3O2[M+]).
Compound VIi
Yellow solid, yield: 53% (> 97% purity, nuclear magnetic purity)
MS(ESI+):641(C26H40ClFIrN3O2[M+]).
Example 5 Synthesis of metallic Iridium Complex represented by formula V
Adding [ Ir (cod) X into a dry 250 ml three-mouth bottle under the protection of argon1d]2(336mg,0.5mmol), a compound represented by the formula e, a base and an organic solvent, stirring to react, and separating the crude product by column chromatography (ethyl acetate/petroleum ether: 1: 5). The specific reaction conditions for compounds Va-Vc and compound Vf are shown in Table 5. The compound Vd-Ve, the preparation method and conditions of compound Vg refer to example 5 and Table 5, wherein the molar ratio in Table 5 refers to [ Ir (cod) X1d]2: compound e: molar ratio of the base.
TABLE 5
Compound Va
Yellow solid, yield: 53% (> 97% purity, nuclear magnetic purity)
MS(ESI+):659(C28H37ClIrN3O[M+]).
Compound Vb
Yellow solid, yield: 55% (> 97% purity, nuclear magnetic purity)
MS(ESI+):701(C31H41ClIrN3O[M+]).
Compound Vc
Yellow solid, yield: 55% (> 97% purity, nuclear magnetic purity)
MS(ESI+):795(C30H35ClF6IrN3O[M+]).
Compound Vd
Yellow solid, yield: 55% (> 97% purity, nuclear magnetic purity)
MS(ESI+):689(C29H39ClIrN3O2[M+]).
Compound Ve
Yellow solid, yield: 55% (> 97% purity, nuclear magnetic purity)
MS(ESI+):749(C28H32ClF5IrN3O[M+]).
Compound Vf
Yellow solid, yield: 55% (> 97% purity, nuclear magnetic purity)
MS(ESI+):655(C29H40IrN3O2[M+]).
Compound Vg
Yellow solid, yield: 55% (> 97% purity, nuclear magnetic purity)
MS(ESI+):595(C23H33IrN3O[M+]).
Example 6 Synthesis of Metal Iridium Complex represented by general formula VI
Adding [ Ir (cod) X into a dry 250 ml three-mouth bottle under the protection of argon1e]2(336mg,0.5mmol) of a compound represented by the formula f, a base and an organic solvent, and the crude product is separated by column chromatography (ethyl acetate/petroleum ether: 1: 5). The specific reaction conditions for compounds VIa-VIc and compound VIf are shown in table 6. The preparation method and conditions of the compound VId-VIe refer to example 6 and Table 6, wherein the molar ratio in Table 6 is [ Ir (cod) X1e]2: a compound f: molar ratio of the base.
TABLE 6
Compound VIa
Yellow solid, yield: 55% (> 97% purity, nuclear magnetic purity)
MS(ESI+):671(C29H37ClIrN3O[M+]).
Compound VIb
Orange solid, yield: 51% (> 97% purity, nuclear magnetic purity)
1H NMR(400MHz,CD2Cl2)δ8.43(d,J＝6.0Hz,1H),7.36-7.32(m,3H),7.07(s,1H),6.95(s,1H),6.91(d,J＝3.2Hz,1H),4.92(AB,JAB＝16.0Hz,1H),4.83(AB,JAB＝16.0Hz,1H),4.74-4.73(m,1H),4.60-4.58(m,1H),4.47-4.43(m,1H),3.34(dd,J＝4.0,16.8Hz,1H),3.23-3.15(m,2H),2.85(t,J＝6.8Hz,1H),2.37(s,6H),2.27-2.18(m,1H),2.15-2.08(m,1H),1.88(s,3H),1.88-1.86(m,1H),1.69-1.63(m,1H),1.54-1.48(m,3H),1.40-1.38(m,1H).
13C NMR(100MHz,CD2Cl2)δ182.1,148.4,140.8,140.1,139.5,136.9,136.7,136.1,129.6,128.9,128.6,126.9,126.0,125.6,87.4,84.6,79.0,62.4,61.2,56.5,52.7,37.7,34.6,33.0,30.3,28.1,21.3,19.7,17.9.
Compound VIc
Yellow solid, yield: 59% (> 97% purity, nuclear magnetic purity)
MS(ESI+):807(C31H35ClF6IrN3O[M+]).
Compound VId
Yellow solid, yield 59% (> 97% purity, nuclear magnetic purity)
MS(ESI+):701(C30H39ClF6IrN3O[M+]).
Compound VIe
Yellow solid, yield: 57% (> 97% purity, nuclear magnetic purity)
1H NMR(400MHz,DMSO-d6)δ8.57(d,J＝8.0Hz,1H),7.36(d,J＝7.6Hz,1H),7.30(t,J＝7.6Hz,1H),7.17(t,J＝7.2Hz,1H),6.02(d,J＝3.2Hz,1H),5.00(AB,JAB＝15.6Hz,1H),4.94(t,J＝3.6Hz,1H),4.91(AB,JAB＝16.0Hz,1H),4.60-4.56(m,1H),4.38-4.35(m,1H),3.46-3.41(m,2H),3.30-3.27(m,1H),3.04(AB,JAB＝16.8Hz,1H)2.13-2.09(m,1H),2.00-1.88(m,3H),1.71-1.58(m,4H).
13C NMR(100MHz,DMSO-d6)δ187.8,149.9,140.8,138.5,128.6,126.6,126.5,125.0,87.8,86.2,78.2,62.0,59.7,54.5,52.9,36.9,33.4,33.0,28.9,28.7,27.6；19F NMR(376MHz,DMSO-d6)δ-138.6(d,J＝23.3Hz),-144.6(d,J＝24.8Hz),-150.3(t,J＝22.6Hz),-161.9(t,J＝23.7Hz),-162.6(t,J＝23.3Hz).
Elemental analysis: calcd for C26H22N3F5ClOIr is C, 43.67; h, 3.10; n,5.88 Experimental values (Found) C, 43.62; h, 3.02; n,5.71.
Compound VIf
Yellow solid, yield: 60% (> 97% purity, nuclear magnetic purity)
MS(ESI+):684(C31H45IrN3O2[M+]).
Effect example 1 Synthesis of Compound represented by the general formula P
General reaction operation: to a Schlenk tube, under protection of argon, substrate S1(75.6mg,0.2mmol), metallo-iridium complex catalyst (3.2mg,0.01mmol,5 mol%) and base (3.0mg,0.02mmol) were added in 2.0mL of dichloromethane (CH)2Cl2) The reaction was stirred at room temperature for 6 hours. After completion of the TLC tracing reaction, the reaction mixture was filtered through celite, and the solvent was removed under reduced pressure and purified by column chromatography (petroleum ether/ethyl acetate: 5/1). The ee of the product was determined by HPLC. Wherein, the conditions of the substrate S1, the catalyst, the alkali and the like are concretely shown in Table 7, and the molar ratio in Table 7 refers to S1: alkali: molar ratio of catalyst. In table 7, the molar ratio is S1: alkali: molar ratio of catalyst.
TABLE 7
Compound P1
Light yellow oil, yield: 81% and an ee value of 92% [ Daicel Chiralcel OD-H, hexane (hexane)/2-propanol (2-propanol) ═ 90/10, v ═ 1.0ml · min-1,λ＝254nm,t(minor)＝20.38min,t(major)＝31.75min].
[α]D 20+6.4(c1.00,CH2Cl2).
1H NMR(300MHz,CDCl3)δ3.43(d,J＝12.6Hz,1H),3.93(dd,J＝12.6,4.5Hz,1H),4.54-4.68(m,2H),4.87-5.00(m,2H),5.08(d,J＝10.5Hz,1H),5.73(ddd,J＝16.8,10.2,5.4Hz,1H),7.15(t,J＝6.9Hz,1H),7.21-7.38(m,8H),7.72(d,J＝7.8Hz,1H).
Compound P2
Yellow solid, yield: 77%, ee value 91% [ Daicel ChiralpakAD-H, hexane (hexane)/2-propanol (2-propanol) ═ 80/20, v ═ 1.0ml · min-1,λ＝254nm,t(major)＝26.51min,t(minor)＝33.90min].
[α]D 16+8.7(c1.00,CH2Cl2).
1H NMR(300MHz,CDCl3)δ3.45(dd,J＝12.6,2.1Hz,1H),3.94(dd,J＝12.9,5.1Hz,1H),4.57(d,J＝16.8Hz,2H),4.59(d,J＝14.7Hz,2H),5.10(d,J＝9.9Hz,1H),5.70(ddd,J＝16.8,10.5,5.4Hz,1H),7.12(d,J＝9.0Hz,1H),7.24-7.40(m,7H),7.85(s,1H)；13C NMR(75MHz,CDCl3)δ49.4,49.5,53.0,105.8,111.5,113.9,118.3,125.0,127.5,127.8,128.5,128.6,128.9,129.6,133.5,134.7,136.1,159.3.
IR (film) < v >max(cm-1)＝3064,1639,1547,1448,1429,1251,1173,933,802,732,697.
HRMS-ESI calculated value (Calcd for) C20H18BrN2O(M++ H) 381.0597, Experimental value (Found) 381.0599.
m.p.＝135-136℃.
Compound P3
Light yellow oil, yield: 78%, ee value 92% [ Daicel ChiralpakAD-H, hexane (hexane)/2-propanol (2-propanol) ═ 80/20, v ═ 1.0ml · min-1,λ＝254nm,t(major)＝17.92min,t(minor)＝24.91min].
[α]D 17+12.3(c1.00,CH2Cl2).
1H NMR(300MHz,CDCl3)δ3.45(d,J＝13.2Hz,1H),3.93(dd,J＝13.2,4.8Hz,1H),4.60(d,J＝14.7Hz,1H),4.62(d,J＝17.1Hz,1H),4.83-4.99(m,2H),5.12(d,J＝10.5Hz,1H),5.72(ddd,J＝15.6,9.9,5.1Hz,1H),7.12(d,J＝8.7Hz,1H),7.25(s,1H),7.27-7.38(m,6H),7.63(d,J＝8.4Hz,1H)；13C NMR(75MHz,CDCl3)δ49.5,49.6,53.0,106.7,110.0,118.4,121.7,123.6,125.9,127.8,128.5,128.6,129.3,130.5,133.4,136.1,136.4,159.5.
IR (film) < v >max(cm-1)＝2918,2850,1652,1645,1564,1471,1347,1057,951,735,700.
HRMS-ESI calculated value (Calcd for) C20H18ClN2O(M++ H) 337.1102, Experimental value (Found) 337.1104.
Compound P4
Yellow solid, yield: 84% and an ee value of 89% [ Daicel ChiralpakAD-H, hexane (hexane)/2-propanol (2-propanol) ═ 80/20, v ═ 1.0ml · min-1,λ＝254nm,t(major)＝20.09min,t(minor)＝25.97min].
[α]D 17+3.1(c1.00,CH2Cl2).
1H NMR(400MHz,CDCl3)δ3.44(d,J＝12.0,1.6Hz,1H),3.92(dd,J＝12.8,4.4Hz,1H),4.57-4.64(m,2H),4.89-4.96(m,2H),5.09(d,J＝10.4Hz,1H),5.72(ddd,J＝16.8,10.4,5.2Hz,1H),7.03(dt,J＝8.8,2.4Hz,1H),7.17(dd,J＝9.2,4.4Hz,1H),7.24-7.36(m,7H).
13C NMR(75MHz,CDCl3)δ49.5,49.6,53.1,106.2,106.3,106.8,107.1,110.9,113.6,118.2,127.5,127.6,127.7,128.4,128.6,130.1,132.8,133.7,136.2,156.9,159.3,159.4.
IR (film) < v >max(cm-1)＝3030,2922,1640,1549,1496,1466,1361,1250,1189,928,800,735.
HRMS-ESI calculated value (Calcd for) C20H18FN2O(M++ H) 321.1398, Experimental value (Found) 321.1398.
m.p.＝127-128℃.
Compound P5
Yellow solid, yield: 86% and an ee value of 93% [ Daicel ChiralpakAD-H, hexane (hexane)/2-propanol (2-propanol) ═ 80/20, v ═ 1.0ml · min-1,λ＝230nm,t(major)＝24.02min,t(minor)＝29.46min].
[α]D 21+7.0(c1.00,CH2Cl2).
1H NMR(400MHz,CDCl3)δ2.43(s,3H),3.42(dd,J＝12.4,2.0Hz,1H),3.92(dd,J＝12.8,4.8Hz,1H),4.57-4.64(m,2H),4.89-4.97(m,2H),5.09(d,J＝10.4Hz,1H),5.72(ddd,J＝15.6,10.0,5.2Hz,1H),7.09-7.16(m,2H),7.24-7.36(m,6H),7.50(s,1H).
13C NMR(75MHz,CDCl3)δ21.4,49.5,49.7,52.9,106.1,109.7,118.0,122.1,126.5,127.6,127.7,128.4,128.5,128.6,130.1,133.9,134.7,136.4,159.9.
IR (film) < v >max(cm-1)＝3053,2919,1635,1549,1428,1357,1253,1184,934,809,737,697.
HRMS-ESI calculated value (Calcd for) C21H21N2O(M++ H) 317.1648, Experimental value (Found) 317.1652.
m.p.＝142-143℃.
Compound P6
White solid, yield: 87% and an ee value of 94% [ Daicel ChiralpakAD-H, hexane (hexane)/2-propanol (2-propanol) ═ 80/20, v ═ 1.0ml · min-1,λ＝230nm,t(major)＝28.39min,t(minor)＝45.66min].
[α]D 20+3.8(c1.00,CH2Cl2).
1H NMR(400MHz,CDCl3)δ3.42(dd,J＝12.4,2.0Hz,1H),3.84(s,3H),3.92(dd,J＝12.4,4.8Hz,1H),4.61(d,J＝14.8Hz,1H),4.62(d,J＝16.8Hz,1H),4.87-4.96(m,2H),5.08(d,J＝10.4Hz,1H),5.72(ddd,J＝15.6,10.4,5.2Hz,1H),6.96(dd,J＝9.2,3.2Hz,1H),7.10-7.16(m,2H),7.24-7.34(m,6H).
13C NMR(75MHz,CDCl3)δ49.4,49.7,53.1,55.6,102.8,106.1,110.9,116.0,118.0,127.6,127.8,128.4,128.6,129.0,131.6,134.0,136.4,154.7,159.8.
IR (film) < v >max(cm-1)＝3065,2935,1633,1545,1358,1230,1215,1034,834,813,703.
HRMS-ESI calculated value (Calcd for) C21H21N2O2(M++ H) 333.1598, Experimental value (Found) 333.1600.
m.p.＝148-149℃.
Compound P7
Colorless oil, yield: 75%, ee value 92% [ Daicel ChiralpakAD-H, hexane (hexane)/2-propanol (2-propanol) ═ 80/20, v ═ 1.0ml · min-1,λ＝230nm,t(major)＝18.96min,t(minor)＝24.65min].
[α]D 16+16.2(c1.00,CH2Cl2).
1H NMR(400MHz,CDCl3)δ3.44(d,J＝12.9Hz,1H),3.92(dd,J＝12.6,4.5Hz,1H),4.59(d,J＝14.7Hz,1H),4.61(d,J＝16.8Hz,1H),4.85-4.98(m,2H),5.12(d,J＝10.8Hz,1H),5.71(ddd,J＝16.2,10.2,5.1Hz,1H),7.20-7.38(m,7H),7.41(s,1H),7.57(d,J＝8.4Hz,1H).
13C NMR(100MHz，CDCl3)δ49.5，49.6，53.0，106.7，113.0，118.3，118.4，123.9，124.2，126.2,127.8,128.5,128.6,129.2,133.4,136.1,136.8,159.4.
IR (film) < v >max(cm-1) 3080,2925,1644,1545,1494,1430,1355,1270,1149,928,821,744; HRMS-ESI calculated value (Calcd for) C20H18BrN2O(M++ H) 381.0597, Experimental value (Found) 381.0599.
Compound P8
Yellow solid, yield: 75%, ee value 91% [ Daicel ChiralpakAD-H, hexane (hexane)/2-propanol (2-propanol) ═ 80/20, v ═ 1.0ml · min-1,λ＝230nm,t(major)＝23.53min,t(minor)＝29.22min]；[α]D 26+10.2(c1.00,CH2Cl2).
1H NMR(400MHz,CDCl3)δ3.45(dd,J＝12.6,1.8Hz,1H),3.94(dd,J＝12.9,5.1Hz,1H),4.53-4.64(m,2H),4.89-4.98(m,2H),5.10(d,J＝9.9Hz,1H),5.71(ddd,J＝15.6,10.5,5.4Hz,1H),7.13-7.19(m,1H),7.20-7.38(m,7H),7.68(s,1H).
13C NMR(75MHz,CDCl3)δ49.5,49.6,53.0,105.9,111.1,118.3,121.9,125.0,126.4,127.8,128.2,128.5,128.6,129.8,133.5,134.4,136.1,159.4.
IR (film) < v >max(cm-1)＝3086,2924,1649,1548,1474,1420,1250,1061,919,801,745.
HRMS-ESI calculated value (Calcd for) C20H18ClN2O(M++ H) 337.1102 Experimental values (Found) 337.1108 m.p.127 and 128 ℃.
Compound P9:
yellow oil, yield: 89% ee value 89% [ Daicel ChiralpakAD-H, hexane (hexane)/2-propanol (2-propanol) ═ 80/20, v ═ 1.0ml · min-1,λ＝230nm,t(major)＝14.51min,t(minor)＝19.40min].
[α]D 25+21.9(c1.00,CH2Cl2).
1H NMR(400MHz,CDCl3)δ3.42(dd,J＝12.9,2.1Hz,1H),3.83(s,3H),3.92(dd,J＝12.6,4.5Hz,1H),4.59(d,J＝15.0Hz,1H),4.61(d,J＝16.5Hz,1H),5.10(d,J＝9.9Hz,1H),5.72(ddd,J＝15.6,10.5,5.1Hz,1H),6.63(s,1H),6.82(dd,J＝8.7,2.1Hz,1H),7.24-7.37(m，6H)，7.59(d，J＝8.7Hz，1H).
13C NMR(75MHz,CDCl3)δ49.4,49.7,52.8,55.5,92.3,107.0,111.7,118.1,121.7,123.5,127.6,127.7,128.5,128.6,133.7,136.5,137.1,158.3,159.9.
IR (film) < v >max(cm-1)＝3292,2924,1640,1544,1496,1312,1210,1028,812,703.
HRMS-ESI calculated value (Calcd for) C21H21N2O2(M++ H) 333.1598, Experimental value (Found) 333.1599.
Compound P10
White solid, yield: 77% and an ee value of 90% [ Daicel Chiralcel OD-H, hexane (hexane)/2-propanol (2-propanol) ═ 80/20, v ═ 1.0ml · min-1,λ＝230nm,t(minor)＝13.30min,t(major)＝27.78min].
[α]D 18-13.9(c1.00,CH2Cl2).1H NMR(400MHz,CDCl3)δ3.15(s,3H),3.50(dd,J＝12.8,2.4Hz,1H),4.08(dd,J＝12.8,4.8Hz,1H),4.76(d,J＝16.0Hz,1H),4.99-5.05(m,1H),5.17(d,J＝10.0Hz,1H),5.95(ddd,J＝15.6,10.0,5.6Hz,1H),7.12-7.18(m,1H),7.24-7.32(m,3H),7.71(d,J＝8.0Hz,1H).
13C NMR(100MHz,CDCl3)δ34.4,52.7,53.0,106.1,110.0,118.2,120.7,122.6,124.4,127.4,128.7,133.8,136.1,160.0.
IR (film) < v >max(cm-1)＝3083,2926,1644,1551,1454,1399,1326,1268,936,812,752,744.
HRMS-ESI calculated value (Calcd for) C14H15N2O(M++ H) 227.1179 Experimental values (Found) 227.1175;
m.p.＝127-128℃.
compound P11
White solid, yield: 82% and an ee value of 92% [ Daicel Chiralcel OD-H, hexane (hexane)/2-propanol (2-propanol) ═ 85/15, v ═ 1.0ml · min-1,λ＝230nm,t(minor)＝16.68min,t(major)＝34.39min]；[α]D 27-22.1(c1.00,CH2Cl2).
1H NMR(300MHz，CDCl3)δ3.51(dd，J＝12.9，2.4Hz，1H)，3.91-4.04(m，2H)，4.40(dd,J＝15.6,5.7Hz,1H),4.69(d,J＝17.4Hz,1H),4.98-5.08(m,1H),5.16(d,J＝10.2Hz,1H),5.25(d,J＝9.3Hz,1H),5.28(d,J＝17.1Hz,1H),5.71-5.98(m,2H),7.11-7.20(m,1H),7.23-7.35(m,3H),7.71(d,J＝7.8Hz,1H).
13C NMR(100MHz,CDCl3)δ48.4,49.6,52.9,106.4,110.0,118.2,118.6,120.7,122.6,124.5,127.4,128.6,132.5,133.8,136.0,159.5.
IR (film) < v >max(cm-1)＝3050,2906,1641,1544,1456,1356,1243,1145,933,921,815,756.
HRMS-ESI calculated value (Calcd for) C16H17N2O(M++ H) 253.1335, Experimental value (Found) 253.1336.
m.p.＝115-116℃.
Compound P12
Light yellow oil, yield: 95% and an ee value of 93% [ Daicel ChiralpakAD-H, hexane (hexane)/2-propanol (2-propanol) ═ 80/20, v ═ 1.0ml · min-1,λ＝230nm,t(major)＝24.83min,t(minor)＝34.87min].
[α]D 17-4.4(c1.00,CH2Cl2).
1H NMR(300MHz,CDCl3)δ3.43(d,J＝13.2Hz,1H),3.78(s,3H),3.94(dd,J＝12.9,5.1Hz,1H),4.52(d,J＝14.7Hz,1H),4.58(d,J＝17.7Hz,1H),4.89(d,J＝14.7Hz,1H),4.94-5.00(m,1H),5.07(d,J＝10.5Hz,1H),5.71(ddd,J＝15.9,10.5,5.4Hz,1H),6.85(d,J＝8.4Hz,1H),7.14(t,J＝7.8Hz,1H),7.21-7.33(m,4H),7.34(s,1H),7.72(d,J＝7.8Hz,1H).
Effect example 2
General reaction operation: to a Schlenk tube, under protection of argon, substrate S1(75.6mg,0.2mmol), 3a (5.8mg,0.01mmol,5 mol%) and DBU (3.0mg,0.02mmol) were added in 2.0mL of dichloromethane (CH)2Cl2) The reaction was stirred at room temperature for 6 hours. After completion of the TLC tracing reaction, the reaction mixture was filtered through celite, and the solvent was removed under reduced pressure and purified by column chromatography (petroleum ether/ethyl acetate: 5/1). The ee of the product was determined by HPLC. In table 8, the molar ratio is S1: alkali: molar ratio of catalyst.
TABLE 8
Compound P13
Light yellow oil, yield: 83% and an ee value of 99% [ Daicel Chiralcel OD-H, hexane (hexane)/2-propanol (2-propanol) ═ 90/10, v ═ 1.0ml · min-1,λ＝254nm,t(major)＝19.86min,t(minor)＝34.51min]；[α]D 28-6.5(c1.00,CH2Cl2).
1H NMR(300MHz,CDCl3)δ3.43(d,J＝12.6Hz,1H),3.93(dd,J＝12.6,4.5Hz,1H),4.54-4.68(m,2H),4.87-5.00(m,2H),5.08(d,J＝10.5Hz,1H),5.73(ddd,J＝16.8,10.2,5.4Hz,1H),7.15(t,J＝6.9Hz,1H),7.21-7.38(m,8H),7.72(d,J＝7.8Hz,1H).
Compound P14
Yellow solid, yield: 87% and an ee value of 98% [ Daicel ChiralpakAD-H, hexane (hexane)/2-propanol (2-propanol) ═ 80/20, v ═ 1.0ml · min-1,λ＝254nm,t(minor)＝23.86min,t(major)＝30.53min].
[α]D 26-10.2(c1.00,CH2Cl2).
1H NMR(300MHz,CDCl3)δ3.45(dd,J＝12.6,2.1Hz,1H),3.94(dd,J＝12.9,5.1Hz,1H),4.57(d,J＝16.8Hz,2H),4.59(d,J＝14.7Hz,2H),5.10(d,J＝9.9Hz,1H),5.70(ddd,J＝16.8,10.5,5.4Hz,1H),7.12(d,J＝9.0Hz,1H),7.24-7.40(m,7H),7.85(s,1H).
13C NMR(75MHz,CDCl3)δ49.4,49.5,53.0,105.8,111.5,113.9,118.3,125.0,127.5,127.8,128.5,128.6,128.9,129.6,133.5,134.7,136.1,159.3.
IR (film) < v >max(cm-1) 3064,1639,1547,1448,1429,1251,1173,933,802,732,697; HRMS-ESI calculated value (Calcd for) C20H18BrN2O(M++ H) 381.0597, Experimental value (Found) 381.0599.
m.p.＝135-136℃.
Compound P15
Light yellow oil, yield: 91%, ee value 98% [ Daicel ChiralpakAD-H, hexane (hexane)/2-propanol (2-propanol) ═ 80/20, v ═ 1.0ml · min-1,λ＝254nm,t(minor)＝16.81min,t(major)＝22.81min].
[α]D 26-13.7(c1.00,CH2Cl2).
1H NMR(300MHz,CDCl3)δ3.45(d,J＝13.2Hz,1H),3.93(dd,J＝13.2,4.8Hz,1H),4.60(d,J＝14.7Hz,1H),4.62(d,J＝17.1Hz,1H),4.83-4.99(m,2H),5.12(d,J＝10.5Hz,1H),5.72(ddd,J＝15.6,9.9,5.1Hz,1H),7.12(d,J＝8.7Hz,1H),7.25(s,1H),7.27-7.38(m,6H),7.63(d,J＝8.4Hz,1H).
13C NMR(75MHz,CDCl3)δ49.5,49.6,53.0,106.7,110.0,118.4,121.7,123.6,125.9,127.8，128.5，128.6，129.3，130.5，133.4，136.1，136.4，159.5.
IR (film) < v >max(cm-1)＝2918,2850,1652,1645,1564,1471,1347,1057,951,735,700.
HRMS-ESI calculated value (Calcd for) C20H18ClN2O(M++ H) 337.1102, Experimental value (Found) 337.1104.
Compound P16
Yellow solid, yield: 84% and an ee value of 98% [ Daicel ChiralpakAD-H, hexane (hexane)/2-propanol (2-propanol) ═ 80/20, v ═ 1.0ml · min-1,λ＝254nm,t(minor)＝18.42min,t(minor)＝23.58min]；[α]D 23-3.7(c1.00,CH2Cl2).
1H NMR(400MHz,CDCl3)δ3.44(d,J＝12.0,1.6Hz,1H),3.92(dd,J＝12.8,4.4Hz,1H),4.57-4.64(m,2H),4.89-4.96(m,2H),5.09(d,J＝10.4Hz,1H),5.72(ddd,J＝16.8,10.4,5.2Hz,1H),7.03(dt,J＝8.8,2.4Hz,1H),7.17(dd,J＝9.2,4.4Hz,1H),7.24-7.36(m,7H)；13C NMR(75MHz,CDCl3)δ49.5,49.6,53.1,106.2,106.3,106.8,107.1,110.9,113.6,118.2,127.5,127.6,127.7,128.4,128.6,130.1,132.8,133.7,136.2,156.9,159.3,159.4.
IR (film) < v >max(cm-1)＝3030,2922,1640,1549,1496,1466,1361,1250,1189,928,800,735.
HRMS-ESI calculated value (Calcd for) C20H18FN2O(M++ H) 321.1398, Experimental value (Found) 321.1398.
m.p.＝127-128℃.
Compound P17
Yellow solid, yield: 87% and an ee value of 99% [ Daicel ChiralpakAD-H, hexane (hexane)/2-propanol (2-propanol) ═ 80/20, v ═ 1.0ml · min-1,λ＝230nm,t(minor)＝22.30min,t(major)＝27.39min].
[α]D 25-5.8(c1.00,CH2Cl2).
1H NMR(400MHz,CDCl3)δ2.43(s,3H),3.42(dd,J＝12.4,2.0Hz,1H),3.92(dd,J＝12.8,4.8Hz,1H),4.57-4.64(m,2H),4.89-4.97(m,2H),5.09(d,J＝10.4Hz,1H),5.72(ddd,J＝15.6，10.0，5.2Hz，1H)，7.09-7.16(m，2H)，7.24-7.36(m，6H)，7.50(s，1H)；13C NMR(75MHz,CDCl3)δ21.4,49.5,49.7,52.9,106.1,109.7,118.0,122.1,126.5,127.6,127.7,128.4,128.5,128.6,130.1,133.9,134.7,136.4,159.9.
IR (film) < v >max(cm-1)＝3053,2919,1635,1549,1428,1357,1253,1184,934,809,737,697.
HRMS-ESI calculated value (Calcd for) C21H21N2O(M++ H) 317.1648, Experimental value (Found) 317.1652.
m.p.＝142-143℃.
Compound P18
White solid, yield: 79% ee value 98% [ Daicel ChiralpakAD-H, hexane (hexane)/2-propanol (2-propanol) ═ 80/20, v ═ 1.0ml · min-1,λ＝230nm,t(minor)＝26.64min,t(major)＝30.33min].
[α]D 23-4.9(c1.00,CH2Cl2).
1H NMR(400MHz,CDCl3)δ3.42(dd,J＝12.4,2.0Hz,1H),3.84(s,3H),3.92(dd,J＝12.4,4.8Hz,1H),4.61(d,J＝14.8Hz,1H),4.62(d,J＝16.8Hz,1H),4.87-4.96(m,2H),5.08(d,J＝10.4Hz,1H),5.72(ddd,J＝15.6,10.4,5.2Hz,1H),6.96(dd,J＝9.2,3.2Hz,1H),7.10-7.16(m,2H),7.24-7.34(m,6H).
13C NMR(75MHz,CDCl3)δ49.4,49.7,53.1,55.6,102.8,106.1,110.9,116.0,118.0,127.6,127.8,128.4,128.6,129.0,131.6,134.0,136.4,154.7,159.8.
IR (film) < v >max(cm-1)＝3065,2935,1633,1545,1358,1230,1215,1034,834,813,703.
HRMS-ESI calculated value (Calcd for) C21H21N2O2(M++ H) 333.1598, Experimental value (Found) 333.1600.
m.p.＝148-149℃.
Compound P19
Colorless oil, yield: 91%, ee value 99% [ Daicel ChiralpakAD-H, hexane/2-propanol (2-propanol) ═ 80/20, v ═ 1.0 ml/min-1，λ＝230nm，t(minor)＝18.25min，t(major)＝23.05min].
[α]D 28-16.6(c1.00,CH2Cl2).
1H NMR(400MHz,CDCl3)δ3.44(d,J＝12.9Hz,1H),3.92(dd,J＝12.6,4.5Hz,1H),4.59(d,J＝14.7Hz,1H),4.61(d,J＝16.8Hz,1H),4.85-4.98(m,2H),5.12(d,J＝10.8Hz,1H),5.71(ddd,J＝16.2,10.2,5.1Hz,1H),7.20-7.38(m,7H),7.41(s,1H),7.57(d,J＝8.4Hz,1H).
13C NMR(100MHz,CDCl3)δ49.5,49.6,53.0,106.7,113.0,118.3,118.4,123.9,124.2,126.2,127.8,128.5,128.6,129.2,133.4,136.1,136.8,159.4.
IR (film) < v >max(cm-1)＝3080,2925,1644,1545,1494,1430,1355,1270,1149,928,821,744.
HRMS-ESI calculated value (Calcd for) C20H18BrN2O(M++ H) 381.0597, Experimental value (Found) 381.0599.
Compound P20
Yellow solid, yield: 86% and an ee value of 98% [ Daicel ChiralpakAD-H, hexane (hexane)/2-propanol (2-propanol) ═ 80/20, v ═ 1.0ml · min-1,λ＝230nm,t(minor)＝21.57min,t(major)＝26.72min].
[α]D 26-9.9(c1.00,CH2Cl2).
1H NMR(400MHz,CDCl3)δ3.45(dd,J＝12.6,1.8Hz,1H),3.94(dd,J＝12.9,5.1Hz,1H),4.53-4.64(m,2H),4.89-4.98(m,2H),5.10(d,J＝9.9Hz,1H),5.71(ddd,J＝15.6,10.5,5.4Hz,1H),7.13-7.19(m,1H),7.20-7.38(m,7H),7.68(s,1H).
13C NMR(75MHz,CDCl3)δ49.5,49.6,53.0,105.9,111.1,118.3,121.9,125.0,126.4,127.8,128.2,128.5,128.6,129.8,133.5,134.4,136.1,159.4.
IR (film) < v >max(cm-1) 3086,2924,1649,1548,1474,1420,1250,1061,919,801,745; HRMS-ESI calculated value (Calcd for) C20H18ClN2O(M++ H) 337.1102, Experimental value (Found) 337.1108.
m.p.＝127-128℃.
Compound P21
Yellow oil, yield: 77%, ee value 98% [ Daicel ChiralpakAD-H, hexane (hexane)/2-propanol (2-propanol) ═ 80/20, v ═ 1.0ml · min-1,λ＝230nm,t(minor)＝22.72min,t(major)＝29.24min].
[α]D 22-24.2(c1.00,CH2Cl2).
1H NMR(400MHz,CDCl3)δ3.42(dd,J＝12.9,2.1Hz,1H),3.83(s,3H),3.92(dd,J＝12.6,4.5Hz,1H),4.59(d,J＝15.0Hz,1H),4.61(d,J＝16.5Hz,1H),5.10(d,J＝9.9Hz,1H),5.72(ddd,J＝15.6,10.5,5.1Hz,1H),6.63(s,1H),6.82(dd,J＝8.7,2.1Hz,1H),7.24-7.37(m,6H),7.59(d,J＝8.7Hz,1H).
13C NMR(75MHz,CDCl3)δ49.4,49.7,52.8,55.5,92.3,107.0,111.7,118.1,121.7,123.5,127.6,127.7,128.5,128.6,133.7,136.5,137.1,158.3,159.9.
IR (film) < v >max(cm-1)＝3292,2924,1640,1544,1496,1312,1210,1028,812,703.
HRMS-ESI calculated value (Calcd for) C21H21N2O2(M++ H) 333.1598, Experimental value (Found) 333.1599.
Compound P22
White solid, yield: 81% ee value 96% [ Daicel Chiralcel OD-H, hexane (hexane)/2-propanol (2-propanol) ═ 80/20, v ═ 1.0ml · min-1,λ＝230nm,t(major)＝11.80min,t(minor)＝25.48min].
[α]D 23+15.8(c1.00,CH2Cl2).1H NMR(400MHz,CDCl3)δ3.15(s,3H),3.50(dd,J＝12.8,2.4Hz,1H),4.08(dd,J＝12.8,4.8Hz,1H),4.76(d,J＝16.0Hz,1H),4.99-5.05(m,1H),5.17(d,J＝10.0Hz,1H),5.95(ddd,J＝15.6,10.0,5.6Hz,1H),7.12-7.18(m,1H),7.24-7.32(m,3H),7.71(d,J＝8.0Hz,1H).
13C NMR(100MHz,CDCl3)δ34.4,52.7,53.0,106.1,110.0,118.2,120.7,122.6,124.4,127.4,128.7,133.8,136.1,160.0.
IR (film) < v >max(cm-1)＝3083,2926,1644,1551,1454,1399,1326,1268,936,812,752,744.
HRMS-ESI calculated value (Calcd for) C14H15N2O(M++ H) 227.1179, Experimental value (Found) 227.1175.
m.p.＝127-128℃.
Compound P23
White solid, yield: 74% and an ee value of 98% [ Daicel Chiralcel OD-H, hexane (hexane)/2-propanol (2-propanol) ═ 85/15, v ═ 1.0ml · min-1,λ＝230nm,t(major)＝15.58min,t(minor)＝31.85min].
[α]D 25+29.7(c1.00,CH2Cl2).
1H NMR(300MHz,CDCl3)δ3.51(dd,J＝12.9,2.4Hz,1H),3.91-4.04(m,2H),4.40(dd,J＝15.6,5.7Hz,1H),4.69(d,J＝17.4Hz,1H),4.98-5.08(m,1H),5.16(d,J＝10.2Hz,1H),5.25(d,J＝9.3Hz,1H),5.28(d,J＝17.1Hz,1H),5.71-5.98(m,2H),7.11-7.20(m,1H),7.23-7.35(m,3H),7.71(d,J＝7.8Hz,1H).
13C NMR(100MHz,CDCl3)δ48.4,49.6,52.9,106.4,110.0,118.2,118.6,120.7,122.6,124.5,127.4,128.6,132.5,133.8,136.0,159.5.
IR (film) < v >max(cm-1)＝3050,2906,1641,1544,1456,1356,1243,1145,933,921,815,756.
HRMS-ESI calculated value (Calcd for) C16H17N2O(M++ H) 253.1335, Experimental value (Found) 253.1336.
m.p.＝115-116℃.
Compound P24
Light yellow oil, yield: 89% ee value of 99% [ Daicel ChiralpakAD-H, hexane (hexane)/2-propanol (2-propanol) ═ 80/20, v ═ 1.0ml · min-1,λ＝230nm,t(minor)＝23.23min,t(major)＝35.43min].
[α]D 28+4.0(c1.00,CH2Cl2).
1H NMR(300MHz，CDCl3)δ3.43(d，J＝13.2Hz，1H)，3.78(s，3H)，3.94(dd，J＝12.9，5.1Hz,1H),4.52(d,J＝14.7Hz,1H),4.58(d,J＝17.7Hz,1H),4.89(d,J＝14.7Hz,1H),4.94-5.00(m,1H),5.07(d,J＝10.5Hz,1H),5.71(ddd,J＝15.9,10.5,5.4Hz,1H),6.85(d,J＝8.4Hz,1H),7.14(t,J＝7.8Hz,1H),7.21-7.33(m,4H),7.34(s,1H),7.72(d,J＝7.8Hz,1H).
Effect example 3 IIIa was left to stand in the air for 6 months and tested for its catalytic action in the synthesis of the compound represented by the formula P
General reaction operation: to a Schlenk tube, under protection of argon, substrate S1(75.6mg,0.2mmol), IIIa (5.8mg,0.01mmol,5 mol% after six months in air) and DBU (3.0mg,0.02mmol) in 2.0mL of dichloromethane (CH)2Cl2) The reaction was stirred at room temperature for 6 hours. After completion of the TLC tracing reaction, the reaction mixture was filtered through celite, and the solvent was removed under reduced pressure and purified by column chromatography (petroleum ether/ethyl acetate: 5/1). The ee of the product was determined by HPLC.
Compound P25
Light yellow oil, yield: 82% and an ee value of 99% [ Daicel Chiralcel OD-H, hexane (hexane)/2-propanol (2-propanol) ═ 90/10, v ═ 1.0ml · min-1,λ＝254nm,t(major)＝19.86min,t(minor)＝34.51min]；[α]D 28-6.5(c1.00,CH2Cl2).
1H NMR(300MHz,CDCl3)δ3.43(d,J＝12.6Hz,1H),3.93(dd,J＝12.6,4.5Hz,1H),4.54-4.68(m,2H),4.87-5.00(m,2H),5.08(d,J＝10.5Hz,1H),5.73(ddd,J＝16.8,10.2,5.4Hz,1H),7.15(t,J＝6.9Hz,1H),7.21-7.38(m,8H),7.72(d,J＝7.8Hz,1H).
Effect example 3
After compounds Ia to Ik, compounds IIa to IIu, compounds IIIa to IIIf, compounds IVa to IVi, compounds Va to Vg and compounds VIa to VIe were placed in the air for 6 months, respectively, the catalytic action of the metal iridium complexes represented by general formulae I to VI of the present invention was determined with reference to the methods for producing the compounds represented by formula P in Effect example 1 and Effect example 2.
TABLE 9
| Compound (I) | Catalyst and process for preparing same | Yield of | ee value (%) | Numbering | Catalyst and process for preparing same | Yield of | ee value (%) |
| P1 | Ia | 81 | 92 | P12 | IVc | 95 | 93 |
| P2 | Ib | 77 | 92 | P14 | IIIa | 87 | 98 |
| P3 | Ik | 78 | 92 | P16 | IIIb | 84 | 98 |
| P4 | Vg | 84 | 89 | P18 | IIIe | 79 | 98 |
| P8 | IIh | 75 | 91 | P23 | IIIf | 74 | 98 |
| P10 | IIk | 77 | 90 | / | / | / | / |
Comparative example 1
To a Schlenk tube, under protection of argon, substrate S1(75.6mg,0.2mmol), 7a (6.6mg,0.01mmol,5 mol%) and DBU (3.0mg,0.02mmol) were added in 2.0mL of dichloromethane (CH)2Cl2) The reaction was stirred at room temperature for 24 hours, and no target product was formed by TLC.
Comparative example 2
To a Schlenk tube, under protection of argon, substrate S1(75.6mg,0.2mmol), 7b (7.6mg,0.01mmol,5 mol%) and DBU (3.0mg,0.02mmol) were added in 2.0mL of dichloromethane (CH)2Cl2) The reaction was stirred at room temperature for 24 hours, and no target product was formed by TLC.
Claims (15)
1. A metal iridium complex represented by a general formula I, a general formula II, a general formula III, a general formula IV, a general formula V or a general formula VI, wherein carbon marked by x is chiral carbon or achiral carbon, and when the carbon is chiral carbon, the chiral carbon is in an S configuration or an R configuration;
wherein R is1、R1a、R1b、R1c、R1dAnd R1eIndependently is C3-C6Cycloalkyl, substituted or unsubstituted C6-C20Aryl of (a);
R2、R2’、R2a、R2a’、R2b、R2b’、R2cand R2c’Independently of one another is hydrogen, C1-C8Alkyl, substituted or unsubstituted C6An aryl group; or R2And R2’And the carbon atoms to which they are attached together form C5-C8Cycloalkyl groups of (a);
R3is composed ofWherein R isaIs C1-C8Perfluoroalkyl group of (1), substituted or unsubstituted C6Aryl of (a); rbIs C1-C8Alkyl of (C)1-C8Alkoxy group of (C)1-C8A perfluoroalkyl group of (a);
R4、R4aand R4bIndependently of one another is hydrogen, C1-C8Alkyl orWherein R isc、Rc' or Rc"independently is C1-C8Alkyl groups of (a);
R5hydrogen, halogen;
X1、X1a、X1b、X1c、X1dand X1eIndependently is halogen or C1-C8Alkoxy group of (a);
wherein, said substituted C6-C20Said substitution in aryl means substitution with one or more of the following substituents: c1-C16Hydrocarbyloxy group of (C)1-C16Alkyl of (C)1-C16When a plurality of substituents are present, the substituents may be the same or different.
2. The metallic iridium complex of formula I, formula II, formula III, formula IV, formula V or formula VI as claimed in claim 1,
when said substituted C6-C20Said substitution in aryl of (A) is by C1-C16When substituted by alkoxy of (A), said C1-C16The alkoxy of (A) is methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy or tert-butoxy;
and/or, when said substituent is C1-C16When there is an alkyl group, said C1-C16The alkyl group of (a) is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl;
and/or, when said substituted C6-C20Said substitution in aryl of (A) is by C1-C16When substituted with fluoroalkyl, said C1-C16By fluoroalkyl is meant C substituted by one or more fluorine atoms1-C16A fluoroalkyl group of (a); said C1-C16The fluoroalkyl group of (a) is trifluoromethyl.
3. The metallic iridium complex of formula I, formula II, formula III, formula IV, formula V or formula VI as claimed in claim 1,
R2、R2’、R2a、R2a’、R2b、R2b’、R2c、R2c’、Rb、R4、R4a、R4b、Rc、Rc’、Rc", said C1-C8The alkyl group of (a) is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl;
and/or, R1、R1a、R1b、R1c、R1d、R1eWherein C is3-C6The cycloalkyl group of (a) is cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl;
and/or, Ra、RbWherein C is1-C8Is perfluoroalkyl of Wherein, including the respective isomeric forms;
and/or, R1、R1a、R1b、R1c、R1d、R1e、R2、R2’、R2a、R2a’、R2b、R2b’、R2c、R2c’、RaAnd said substituted or unsubstituted C6-C20Aryl of (a) is substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted 9-anthracenyl, or substituted or unsubstituted 9-phenanthrenyl; said substituted phenyl is
And/or, Rb、X1、X1a、X1b、X1c、X1dAnd X1eIn (b), the C1-C8Alkoxy of (a) is methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy or tert-butoxy;
and/or, X1、X1a、X1b、X1c、X1dAnd X1eWherein said halogen is fluorine, chlorine, bromine or iodine;
and/or when R2And R2’And the carbon atoms to which they are attached together form C5-C8In the case of a cycloalkyl group of (A), said C5-C8The cycloalkyl group of (a) is cyclopentyl or cyclohexyl.
4. The iridium metal complex of formula II, formula III, formula IV or formula V according to claim 1,
R3in (1), the
And/or, R3In (1), the
And/or, R4In (1), the
5. The metallic iridium complex of formula I, formula II, formula III, formula IV, formula V or formula VI as claimed in claim 1,
in the metal-based complex of the general formula I, R1Is C3-C6Cycloalkyl or substituted or unsubstituted C6-C20Aryl of (a); x1Is halogen or C1-C8Alkoxy group of (a);
and/or, in the metal complex of the formula II, R1aIs C3-C6Cycloalkyl or substituted or unsubstituted C6-C20Aryl of (a); r2And R2’Independently is substituted or unsubstituted C6Aryl of (a); or R2And R2’And the carbon atoms to which they are attached together form C5-C8Cycloalkyl groups of (a); r3Is composed ofWherein R isaIs C1-C8Perfluoroalkyl group of (1), substituted or unsubstituted C6Aryl of (a); rbIs C1-C8Alkyl of (C)1-C8Alkoxy group of (C)1-C8A perfluoroalkyl group of (a); x1aIs halogen or C1-C8Alkoxy group of (a);
and/or, in the metal complex of the formula III, R1bIs substituted or unsubstituted C6Aryl of (a); r2a、R2a’And R4Independently is C1-C8Alkyl groups of (a); x1bIs halogen;
and/or, in the metal complex of the formula IV, R1cIs substituted or unsubstituted C6Aryl of (a); r2bAnd R2b’Independently is C1-C8Alkyl, substituted or unsubstituted C6Aryl of (a); r4aIndependently is C1-C8Alkyl orWherein R isc、Rc' and Rc"independently is C1-C8Alkyl groups of (a); r5Is hydrogen or halogen; x1cIs halogen or C1-C8Alkoxy group of (a);
and/or, in the metal complex of the formula V, R1dIs substituted or unsubstituted C6Aryl of (a); r2c、R2c’And R4bIndependently of one another is hydrogen, C1-C8Alkyl, substituted or unsubstituted C6Aryl of (a); x1dIs halogen or C1-C8Alkoxy group of (a);
and/or, in the metal complex of the formula VI, R1eIs substituted or unsubstituted C6Aryl of (a); x1eIs halogen or C1-C8Alkoxy group of (2).
6. The iridium metal complex of claim 1, wherein the iridium metal complex of formula I is any one of the following compounds:
a metal-based complex represented by the general formula II, which is any one of the following compounds:
a metal-based complex represented by the general formula III, which is any one of the following compounds:
a metal-based complex of formula IV, which is any one of the following compounds:
a metal-based complex represented by formula V, which is any one of the following compounds:
a metal-based complex of formula VI, which is of any of the following structures:
7. a metal iridium complex IIIa single crystal characterized in that, in a single crystal X-ray diffraction spectrum using a radiation source Cu-K α, the crystal is monoclinic, space group is P21, and unit cell parameters thereof are as follows: α -90 °, β -92.5300 (10 °), γ -90 °, unit cell volumeThe number of asymmetric units in the unit cell, Z, is 2;
8. the method for producing a single crystal of the metal iridium complex IIIa according to claim 7, comprising the steps of: and (3) mixing the metal iridium complex IIIa and a benign solvent, then dropwise adding the poor solvent until turbidity just appears, dropwise adding the benign solvent, and standing.
9. A method for preparing the iridium metal complex of formula I, formula II, formula III, formula IV, formula V or formula VI as claimed in any of claims 1 to 6, comprising the steps of: in an organic solvent, in the presence of alkali, a compound shown as a formula a and [ Ir (cod) X1]2A compound represented by the formula b and [ Ir (cod) X1a]2A compound represented by the formula c and [ Ir (cod) X1b]2A compound represented by the formula d and [ Ir (cod) X1c]2A compound represented by the formula e and [ Ir (cod) X1d]2Or a compound of formula f with [ Ir (cod) X1e]2Carrying out a complexation reaction as shown below; respectively preparing metal iridium complexes shown in a general formula I, a general formula II, a general formula III, a general formula IV, a general formula V or a general formula VI;
wherein, the symbols, the groups are defined as in any one of claims 1 to 6; y is halogen, CF3SO3、OTf、BF4Or ClO4。
10. The method according to claim 9, wherein the organic solvent is one or more of an aromatic hydrocarbon solvent, a halogenated hydrocarbon solvent, an ether solvent, an amide solvent, an alkane solvent and a nitrile solvent; the aromatic hydrocarbon solvent is preferably one or more of benzene, toluene and xylene; the halogenated hydrocarbon solvent is preferably one or more of carbon tetrachloride, dichloromethane and trichloromethane; the ether solvent is preferably one or more of tetrahydrofuran, diethyl ether and 1, 4-dioxane; the amide solvent is preferably N, N-dimethylformamide; the alkane solvent is preferably one or more of cyclohexane, n-pentane, n-hexane and n-heptane; the nitrile solvent is preferably acetonitrile;
and/or the base is an inorganic base or an organic base, and the inorganic base is preferably one or more of sodium carbonate, potassium carbonate, cesium carbonate, potassium phosphate, sodium hydride, sodium methoxide, sodium ethoxide, sodium acetate, potassium tert-butoxide, sodium tert-butoxide and lithium tert-butoxide; the organic base is preferably one or more of triethylamine, piperidine, pyridine, N-lutidine and 2, 6-lutidine;
and/or, said [ Ir (cod) X1]2And a compound shown as a formula [ Ir (cod) X1a]2And a compound represented by the formula b, [ Ir (cod) X1b]2And a compound represented by the formula c, [ Ir (cod) X1c]2And a compound represented by the formula d, [ Ir (cod) X1d]2And a compound represented by the formula e or [ Ir (cod) X1e]2The mol ratio of the compound to the compound shown as the formula f is 1:1-1: 3.5; preferably 1:2 to 1: 3.5;
and/or, said [ Ir (cod) X1]2、[Ir(cod)X1a]2、[Ir(cod)X1b]2、[Ir(cod)X1c]2、[Ir(cod)X1d]2Or [ Ir (cod) X1e]2The molar ratio of the alkali to the alkali is 1:1-1: 20; preferably 2:15 to 1: 20;
and/or the organic solvent is reacted with [ Ir (cod) X1]2、[Ir(cod)X1a]2、[Ir(cod)X1b]2、[Ir(cod)X1c]2、[Ir(cod)X1d]2Or [ Ir (cod) X1e]2The volume-mass ratio of (A) is 0.1mL/mg to 1 mL/mg;
and/or the temperature of the complexation reaction is 0-150 ℃; preferably 25 ℃ to 125 ℃;
and/or the time of the complexation reaction is 24-48 hours.
11. Use of the iridium metal complex of formula I, formula II, formula III, formula IV, formula V or formula VI as claimed in any of claims 1 to 6 as a catalyst in asymmetric allyl substitution reactions.
12. The use of claim 11, wherein said asymmetric allylic substitution reaction comprises the steps of: in an organic solvent, under the action of alkali, and under the catalysis of one or more of the metal iridium complexes shown in the general formula I, the general formula II, the general formula III, the general formula IV, the general formula V or the general formula VI in any one of claims 1 to 6, carrying out asymmetric allyl substitution reaction shown in the following formula S1 on the compound shown in the formula S1 to prepare a benzindole compound shown in the formula P; wherein, the carbon marked by the letter is chiral carbon or non-chiral carbon, and when the carbon is chiral carbon, the chiral carbon is in S configuration or R configuration;
in the compound shown as the formula S1 and the compound shown as the formula P, Ra1Is mono-or polysubstituted, the same or different, selected from one or more of the following substituents: halogen, substituted or unsubstituted C1-C4Or substituted or unsubstituted C1-C4Alkoxy group of (a); rb1Is substituted or unsubstituted C1-C4Or substituted or unsubstituted C2-C4Alkenyl of (a); rc1Is composed ofWherein M is NH or O; rd1Is C1-C4Alkyl, C substituted by one or more halogens1-C4Alkyl or C1-C4Alkoxy group of (a); re1Is C1-C4Alkyl or C6-C20An aryl group; ra1And Rb1In (b), said substituted C1-C4Alkyl of (2) or said substituted C1-C4The substituent in the alkoxy group of (a) means a substituent substituted with one or more of the following substituents: halogen, C1-C4Alkoxy group of (C)1-C4Alkyl of (C)6～C20Aryl radicals, or substituted by one or more C1-C4Alkoxy-substituted C6-C20And when the substituent is a plurality of the aryl groups, the substituents are the same or different.
13. The use according to claim 12,
when said substituted C1-C4Alkyl of (2) or said substituted C1-C4When said substitution in said alkoxy group of (a) is by halogen, said halogen is F, Cl, Br or I;
when said substituted C1-C4Alkyl of (2) or said substituted C1-C4Said substitution in alkoxy of (A) is by C1-C4When substituted by alkoxy of (A), said C1-C4Alkoxy of (a) is methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy or tert-butoxy;
when said substituted C1-C4Alkyl of (2) or said substituted C1-C4Said substitution in alkoxy of (A) is by C1-C4When substituted with an alkyl group of (A), said C1-C4The alkyl group of (a) is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl;
when said substituted C1-C4Alkyl of (2) or said substituted C1-C4Said substitution in alkoxy of (a) is by C6～C20When aryl is substituted, said C6～C20Aryl is phenyl;
when said substituted C1-C4Alkyl of (2) or said substituted C1-C4Said substitution in alkoxy of (a) is by one or more C1-C4Alkoxy-substituted C6-C20When substituted by aryl, said group is substituted by one or more C1-C4Alkoxy-substituted C6-C20Aryl is p-methoxyphenyl.
14. The use according to claim 12,
Ra1wherein the halogen is F, Cl, Br or I;
and/or, Ra1Wherein said substituted or unsubstituted C1-C4The alkyl group of (a) is a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted n-propyl group, a substituted or unsubstituted isopropyl group, a substituted or unsubstituted n-butyl group, a substituted or unsubstituted isobutyl group, or a substituted or unsubstituted tert-butyl group; the substituted methyl is benzyl or p-methoxybenzyl;
and/or, Ra1Wherein said substituted or unsubstituted C1-C4The alkoxy group of (a) is a substituted or unsubstituted methoxy group, a substituted or unsubstituted ethoxy group, a substituted or unsubstituted n-propoxy group, a substituted or unsubstituted isopropoxy group, a substituted or unsubstituted n-butoxy group, a substituted or unsubstituted isobutoxy group, or a substituted or unsubstituted tert-butoxy group;
and/or, Rb1In (b), the C2-C4The alkenyl group of (A) is ethenyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl or 3-butenyl;
and/or, Rd1Or Re1In (b), the C1-C4The alkyl group of (a) is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl;
and/or, Rd1Wherein said C is substituted by one or more halogens1-C4The halogen in the alkyl group of (a) means fluorine, chlorine, bromine or iodine; said C substituted by one or more halogens1-C4C in the alkyl group of (1)1-C4The alkyl group of (a) is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl; said C substituted by one or more halogens1-C4The alkyl group of (A) is preferably
And/or, Rd1In (b), the C1-C4Alkoxy of (a) is methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy or tert-butoxy;
and/or, Re1In (1), theC6-C20Aryl is phenyl.
15. The use according to claim 12, wherein in the asymmetric allyl substitution reaction, the organic solvent is one or more of an aromatic hydrocarbon solvent, a halogenated hydrocarbon solvent, an ether solvent, an amide solvent, an alkane solvent and a nitrile solvent; the aromatic hydrocarbon solvent is preferably toluene; the halogenated hydrocarbon solvent is preferably dichloromethane and/or trichloromethane; the ether solvent is preferably one or more of tetrahydrofuran, diethyl ether and 1, 4-dioxane; the alkane solvent is preferably n-hexane; the nitrile solvent is preferably acetonitrile;
and/or the base is an organic base and/or an inorganic base, the organic base preferably being 1, 8-diazabicycloundecen-7-ene, N-diisopropylethylamine, triethylamine and 1, 4-diazabicyclo [2.2.2]One or more of octane; the inorganic base is preferably Cs2CO3、K2CO3、Na2CO3、Li2CO3One or more of lithium tert-butoxide, sodium tert-butoxide and potassium tert-butoxide.
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| CN103254251A (en) * | 2013-05-23 | 2013-08-21 | 中国科学院上海有机化学研究所 | Pi-allyl iridium complex containing dinaphthyl [1,2-b;5,6-b'] cyclooctatetraene and chiral phosphine nitrogen framework as well as synthesizing method and application of complex |
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| WO2009065856A1 (en) * | 2007-11-22 | 2009-05-28 | Universiteit Van Amsterdam | Coordination complex system comprising tautomeric ligands |
| CN103254251A (en) * | 2013-05-23 | 2013-08-21 | 中国科学院上海有机化学研究所 | Pi-allyl iridium complex containing dinaphthyl [1,2-b;5,6-b'] cyclooctatetraene and chiral phosphine nitrogen framework as well as synthesizing method and application of complex |
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| Title |
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| Palladium-Catalyzed Dynamic Kinetic Asymmetric Transformations of Vinyl Aziridines with Nitrogen Heterocycles: Rapid Access to Biologically Active Pyrroles and Indoles;Barry M. Trost等，;《J. AM. CHEM. SOC.》;20101015;第132卷;第15800–15807页，尤其是第15804页表4化合物5c * |
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