CN114989137B - 一种手性含亚胺喹啉咪唑啉类化合物及其金属络合物以及制备方法和应用 - Google Patents
一种手性含亚胺喹啉咪唑啉类化合物及其金属络合物以及制备方法和应用 Download PDFInfo
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- CN114989137B CN114989137B CN202210730077.9A CN202210730077A CN114989137B CN 114989137 B CN114989137 B CN 114989137B CN 202210730077 A CN202210730077 A CN 202210730077A CN 114989137 B CN114989137 B CN 114989137B
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- imine
- quinoline
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- -1 quinoline imidazoline compound Chemical class 0.000 title claims abstract description 109
- 150000004696 coordination complex Chemical class 0.000 title claims abstract description 42
- 150000002466 imines Chemical class 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 230000003287 optical effect Effects 0.000 claims abstract description 23
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 57
- 238000006243 chemical reaction Methods 0.000 claims description 39
- 125000001424 substituent group Chemical group 0.000 claims description 30
- 229910052757 nitrogen Inorganic materials 0.000 claims description 29
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 28
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 14
- 125000000229 (C1-C4)alkoxy group Chemical group 0.000 claims description 13
- 239000003446 ligand Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 125000004178 (C1-C4) alkyl group Chemical group 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
- 238000009876 asymmetric hydrogenation reaction Methods 0.000 claims description 11
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 11
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 11
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 10
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 10
- 125000001624 naphthyl group Chemical group 0.000 claims description 10
- 150000003624 transition metals Chemical class 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 9
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052731 fluorine Inorganic materials 0.000 claims description 7
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 7
- LKZVJKCSPGCLCH-UHFFFAOYSA-N 4,5-dihydro-1h-imidazole;quinoline Chemical compound C1CN=CN1.N1=CC=CC2=CC=CC=C21 LKZVJKCSPGCLCH-UHFFFAOYSA-N 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 150000001879 copper Chemical class 0.000 claims description 5
- 150000007530 organic bases Chemical class 0.000 claims description 5
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 5
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 claims description 5
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical group C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 claims description 4
- 238000005859 coupling reaction Methods 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 229910052741 iridium Inorganic materials 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- 229910000077 silane Inorganic materials 0.000 claims description 3
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 2
- LBLYYCQCTBFVLH-UHFFFAOYSA-M 2-methylbenzenesulfonate Chemical compound CC1=CC=CC=C1S([O-])(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-M 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-M Methanesulfonate Chemical compound CS([O-])(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-M 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-M benzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-M 0.000 claims description 2
- 238000010668 complexation reaction Methods 0.000 claims description 2
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical group I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 2
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- 239000012948 isocyanate Substances 0.000 claims description 2
- 150000002513 isocyanates Chemical class 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- VYGSFTVYZHNGBU-UHFFFAOYSA-N trichloromethanesulfonic acid Chemical compound OS(=O)(=O)C(Cl)(Cl)Cl VYGSFTVYZHNGBU-UHFFFAOYSA-N 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 abstract description 2
- 239000002815 homogeneous catalyst Substances 0.000 abstract description 2
- 230000000536 complexating effect Effects 0.000 abstract 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 36
- 238000005481 NMR spectroscopy Methods 0.000 description 34
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 25
- 239000000047 product Substances 0.000 description 24
- 238000010992 reflux Methods 0.000 description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 239000002904 solvent Substances 0.000 description 18
- 238000001035 drying Methods 0.000 description 17
- 238000004440 column chromatography Methods 0.000 description 16
- 238000005406 washing Methods 0.000 description 16
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 15
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 15
- 235000011114 ammonium hydroxide Nutrition 0.000 description 15
- 239000003480 eluent Substances 0.000 description 15
- 238000003756 stirring Methods 0.000 description 15
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 14
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 14
- 238000002390 rotary evaporation Methods 0.000 description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- 125000003118 aryl group Chemical group 0.000 description 11
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 description 10
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 9
- UFFBMTHBGFGIHF-UHFFFAOYSA-N 2,6-dimethylaniline Chemical compound CC1=CC=CC(C)=C1N UFFBMTHBGFGIHF-UHFFFAOYSA-N 0.000 description 8
- JCZCFNGKDJIKQI-UHFFFAOYSA-N 8-bromoquinolin-2-amine Chemical compound C1=CC=C(Br)C2=NC(N)=CC=C21 JCZCFNGKDJIKQI-UHFFFAOYSA-N 0.000 description 8
- 125000003545 alkoxy group Chemical group 0.000 description 8
- 150000001336 alkenes Chemical class 0.000 description 7
- CJAOGSCDGJDDNL-PCLIKHOPSA-N CC(C)c1cccc(C(C)C)c1\N=C(/C)c1ccc2cccc(Br)c2n1 Chemical compound CC(C)c1cccc(C(C)C)c1\N=C(/C)c1ccc2cccc(Br)c2n1 CJAOGSCDGJDDNL-PCLIKHOPSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- 125000004428 fluoroalkoxy group Chemical group 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 238000005984 hydrogenation reaction Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- DJOBCHKHUAOIRZ-KGENOOAVSA-N C/C(\C1=NC(C(Br)=CC=C2)=C2C=C1)=N\C1=C(C)C=CC=C1C Chemical compound C/C(\C1=NC(C(Br)=CC=C2)=C2C=C1)=N\C1=C(C)C=CC=C1C DJOBCHKHUAOIRZ-KGENOOAVSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- MPAYEWNVIPXRDP-UHFFFAOYSA-N ethanimine Chemical compound CC=N MPAYEWNVIPXRDP-UHFFFAOYSA-N 0.000 description 4
- 229960002089 ferrous chloride Drugs 0.000 description 4
- 125000003709 fluoroalkyl group Chemical group 0.000 description 4
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- OHIHMPVFJYMEIG-UHFFFAOYSA-N 1-phenyl-2-propan-2-yl-4,5-dihydroimidazole Chemical group CC(C)C1=NCCN1C1=CC=CC=C1 OHIHMPVFJYMEIG-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- RFRRSHWJBPVXBR-UHFFFAOYSA-N 1-(8-bromoquinolin-2-yl)ethanone Chemical compound C1=CC=C(Br)C2=NC(C(=O)C)=CC=C21 RFRRSHWJBPVXBR-UHFFFAOYSA-N 0.000 description 2
- FSYYWGUSJBHGCX-UHFFFAOYSA-N 2-tert-butyl-1-phenyl-4,5-dihydroimidazole Chemical group CC(C)(C)C1=NCCN1c1ccccc1 FSYYWGUSJBHGCX-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 101100030361 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) pph-3 gene Proteins 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 150000002462 imidazolines Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- YTJSFYQNRXLOIC-UHFFFAOYSA-N octadecylsilane Chemical compound CCCCCCCCCCCCCCCCCC[SiH3] YTJSFYQNRXLOIC-UHFFFAOYSA-N 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- GCMNJUJAKQGROZ-UHFFFAOYSA-N 1,2-Dihydroquinolin-2-imine Chemical compound C1=CC=CC2=NC(N)=CC=C21 GCMNJUJAKQGROZ-UHFFFAOYSA-N 0.000 description 1
- VPDDVSNZBDNXQZ-UHFFFAOYSA-N 1,2-di(propan-2-yl)-4,5-dihydroimidazole Chemical group CC(C)N1CCN=C1C(C)C VPDDVSNZBDNXQZ-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- REJGDSCBQPJPQT-UHFFFAOYSA-N 2,4,6-tri-tert-butylaniline Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=C(N)C(C(C)(C)C)=C1 REJGDSCBQPJPQT-UHFFFAOYSA-N 0.000 description 1
- WKBALTUBRZPIPZ-UHFFFAOYSA-N 2,6-di(propan-2-yl)aniline Chemical compound CC(C)C1=CC=CC(C(C)C)=C1N WKBALTUBRZPIPZ-UHFFFAOYSA-N 0.000 description 1
- FOYHNROGBXVLLX-UHFFFAOYSA-N 2,6-diethylaniline Chemical compound CCC1=CC=CC(CC)=C1N FOYHNROGBXVLLX-UHFFFAOYSA-N 0.000 description 1
- 125000006276 2-bromophenyl group Chemical group [H]C1=C([H])C(Br)=C(*)C([H])=C1[H] 0.000 description 1
- XJZMENOGBUCBJX-UHFFFAOYSA-N 2-ethyl-1-phenyl-4,5-dihydroimidazole Chemical group CCC1=NCCN1C1=CC=CC=C1 XJZMENOGBUCBJX-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- ZVFRHLNVPIDOTI-UHFFFAOYSA-N 4-methoxy-2,6-di(propan-2-yl)aniline Chemical compound COC1=CC(C(C)C)=C(N)C(C(C)C)=C1 ZVFRHLNVPIDOTI-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 125000006539 C12 alkyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 241000370001 Hantavirus Liu Species 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
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- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- SQQXRXKYTKFFSM-UHFFFAOYSA-N chembl1992147 Chemical compound OC1=C(OC)C(OC)=CC=C1C1=C(C)C(C(O)=O)=NC(C=2N=C3C4=NC(C)(C)N=C4C(OC)=C(O)C3=CC=2)=C1N SQQXRXKYTKFFSM-UHFFFAOYSA-N 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229940052810 complex b Drugs 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000013355 food flavoring agent Nutrition 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000002636 imidazolinyl group Chemical group 0.000 description 1
- 229940124669 imidazoquinoline Drugs 0.000 description 1
- 125000000879 imine group Chemical group 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000010813 internal standard method Methods 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 150000004698 iron complex Chemical class 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
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Abstract
本发明公开了一种手性含亚胺喹啉咪唑啉类化合物,所述的化合物是高光学纯的,结构式如下式(1)所示,并公开了其制备方法。本发明还公开了手性含亚胺喹啉咪唑啉类化合物与过渡金属盐络合得到的的金属络合物,如式(6)所示。本发明还提供所述手性含亚胺喹啉咪唑啉类化合物的金属络合物作为均相催化剂的用途,催化剂通过对烷基烯烃的催化氢化可以用于制备手性或非手性的烷基化合物,特别可用于制备高区域选择性和光学选择性的手性产物,手性产物的对映选择性可达85%以上。
Description
技术领域
本发明涉及一种手性含亚胺喹啉咪唑啉类化合物及其金属络合物以及制备方法,含亚胺喹啉咪唑啉类化合物的金属络合物作为催化剂在1,1-二烷基烯烃的不对称氢化反应中的应用。
背景技术
过渡金属催化的不对称反应是有机合成中最重要的制备手性化合物的方法之一,其在工业生产及学术研究中有着广泛的应用。其中关键的问题是与金属配位的手性配体的设计与合成。手性咪唑啉在手性配体中是一类重要的配体骨架,由手性咪唑啉制得的配体在很多不对称反应中均有应用[(a)J.Li,B.Yu,Z.Lu,Chin.J.Chem.2021,39,488-514;(b)H.Liu,D.-M.Du,Adv.Synth.Catal.2009,351,489–519;(c)F.Menges,M.Neuburger,A.Pfaltz,Org.Lett.2002,4,4713–4716]。因此,基于手性咪唑啉砌块构建不同的手性配体骨架是化学家们一直以来重要的研究方向[(a)Z.Yuan,L.Mei,Y.Wei,M.Shi,P.V.Kattamuri,P.McDowell,G.Li,Org.Biomol.Chem.2012,10,2509–2513;(b)B.Su,T.Lee,J.F.Hartwig,J.Am.Chem.Soc.2018,140,18032–18038;X.Wu,J.Qu,Y.Chen,J.Am.Chem.Soc.2020,142,15654–15660;(c)X.Cheng,H.Lu,Z.Lu,Nat.Commun.2019,10,3549]。
过渡金属催化的烯烃的不对称氢化反应是合成手性化合物最重要的方法之一[(a)W.S.Knowles,Angew.Chem.Int.Ed.2002,41,1998;(b)R.Noyori,Angew.Chem.Int.Ed.2002,41,2008.],而手性烷基化产物在药物分子中有着广泛的应用[(a)S.Bell,B.Wustenberg,S.Kaiser,F.Menges,T.Netscher,A.Pfaltz,Science 2006,311,642–644;(b)X.Cui,K.Burgess,Chem.Rev.2005,105,3272–3296]。目前烯烃的不对称氢化反应主要是贵金属催化体系占主导地位,而贵金属铑、钌、铱等储量稀少,价格昂贵。铁、钴等廉价金属由于其储量丰富,价格便宜,毒性较小,逐渐受到化学家的广泛关注。目前,适用于廉价金属的手性配体的研究还相对较少,催化不对称氢化的底物范围仍然具有较大的局限性。专利CN112851479A公开了一种铁络合物催化剂催化烯烃的不对称氢化反应制备手性烷基化合物的方法,该方法中针对的底物主要是苯乙烯类化合物,对于烷基烯烃的不对称氢化反应,反应的收率和选择性都较差,有待进一步改进。
因此,设计新的适用于廉价金属的手性配体骨架及催化剂,发展新的廉价金属不对称氢化催化模式具有非常重要的意义。
发明内容
为了克服上述所说的现有技术缺陷,本发明人对此进行了深入研究,在经过反复的实验与验证之后,完成了本发明。
本发明公开了一种含亚胺喹啉咪唑啉类化合物及其制备方法,咪唑啉环中的N-R11所在的碳原子与喹啉8号位相连,喹啉2号位与亚胺基团相连。本发明还公开了含亚胺喹啉咪唑啉类化合物的金属络合物;并且涉及该金属络合物作为催化剂在对映体选择性的化学反应中,特别在1,1-二烷基烯烃的不对称氢化反应中具有较好的催化作用。
本发明是通过以下技术方案来实现的:
一种手性含亚胺喹啉咪唑啉类化合物,所述的化合物是高光学纯的,结构式如下式(1)所示:
其中R1是未被取代的或被1-2个C1-C4烷氧基取代的C1-C12烷基、未被取代的或被1-3个取代基A取代的C5~C12的环烷基、或是未被取代的或被1-4个取代基B取代的芳基A;所述芳基A为苄基、苯基或萘基;所述取代基A为C1-C4烷基或C1-C4烷氧基;所述取代基B为C1-C4烷基、C1-C4烷氧基、C1-C4氟烷基、C1-C4氟烷氧基、F或Cl;
R2是H、未被取代的或被1-2个C1-C4烷氧基取代的C1-C12烷基、未被取代的或被1-3个取代基A取代的C5~C12的环烷基、或是未被取代的或被1-3个取代基B取代的芳基B;所述芳基B为苯基或萘基;所述取代基A为C1-C4烷基或C1-C4烷氧基;所述取代基B为C1-C4烷基、C1-C4烷氧基、C1-C4氟烷基、C1-C4氟烷氧基、F或Cl;
R3、R4、R5、R6、R7各自独立为H、C1-C12烷基、C1-C4氟烷氧基、F、Cl、硝基或是未被取代的或被1-3个取代基A取代的C5~C12的环烷基,所述取代基A为C1-C4烷基或C1-C4烷氧基;
R8、R9各自独立为H、未被取代的或被1-2个C1-C4烷氧基取代的C1-C12烷基、未被取代的或被1-3个取代基A取代的C5~C12的环烷基、或是未被取代的或被1-3个取代基B取代的芳基A;所述芳基A为苄基、苯基或萘基;所述取代基A为C1-C4烷基或C1-C4烷氧基;所述取代基B为C1-C4烷基、C1-C4烷氧基、C1-C4氟烷基、C1-C4氟烷氧基、F或Cl;
R10是未被取代的或被1-2个C1-C4烷氧基取代的C1-C12烷基、未被取代的或被1-3个取代基A取代的C5~C12的环烷基、或是未被取代的或被1-3个取代基B取代的芳基A;所述芳基A为苄基、苯基或萘基;所述取代基A为C1-C4烷基或C1-C4烷氧基;所述取代基B为C1-C4烷基、C1-C4烷氧基、C1-C4氟烷基、C1-C4氟烷氧基、F或Cl;
R11是C1-C4烷基、苄基、苯基或萘基。
式(1)中,*代表手性碳原子。
本发明提供的手性含亚胺喹啉咪唑啉的化合物为高光学纯的,所述高光学纯是指有90%以上、优选95%以上、更优选99%以上的对映体选择性。
作为进一步地改进,本发明所述的R1优选为未被取代的或被1-3个取代基A取代的环戊基或环己基、或是未被取代的或被1-4个取代基B取代的芳基A;更优选为未被取代的或被1-3个取代基B取代的苯基,所述取代基B优选为C1-C4烷基或C1-C4烷氧基;R1更优选为2,6-二甲基苯基、2,6-二乙基苯基、2,6-二异丙基苯基或2,6-二异丙基-4-甲氧基苯基。
R2优选为未被取代的或被1-2个C1-C4烷氧基取代的C1-C12烷基或是未被取代的或被1-3个取代基B取代的芳基B;更优选为C1-C12烷基,更优选为甲基、乙基、异丙基或叔丁基;
优选R3、R4、R5、R6、R7各自独立为H或C1-C12烷基,更优选为H、甲基、乙基、异丙基或叔丁基;更优选R3、R4、R5、R6、R7均为H。
优选R8、R9各自独立为H、未被取代的或被1-2个C1-C4烷氧基取代的C1-C12烷基,更优选R8、R9为H、甲基、乙基、异丙基或叔丁基;更优选R8、R9均为H。
优选R10是未被取代的或被1-2个C1-C4烷氧基取代的C1-C12烷基、C5~C12的环烷基或未被取代的或被1-3个取代基B取代的芳基A;更优选为R10为C1-C12烷基、环己基、苯基或苄基,更优选为乙基、异丙基、叔丁基、仲丁基、环己基或苄基。
优选R11是异丙基、苄基、苯基或萘基,更优选为苯基或苄基。
更进一步,优选所述手性含亚胺喹啉咪唑啉类化合物为以下之一:
本发明还公开了式(1)所示的手性含亚胺喹啉咪唑啉类化合物的制备方法,所述的方法为:
氮气保护下,式(4)所示的化合物与式(5)所示的咪唑啉类化合物在过渡金属无机盐和有机膦配体、有机碱、一价铜盐催化下进行偶联反应,制得式(1)所示的手性含亚胺喹啉咪唑啉类化合物。
R1~R11的定义如前所述。
所述过渡金属无机盐是指Ru、Rh、Pd、Ir的无机盐,优选醋酸钯。所述有机碱优选为1,8-二氮杂双环[5.4.0]十一碳-7-烯(DBU);所述有机膦配体优选三苯基膦,一价铜盐优选为碘化亚铜。
所述偶联反应在有机溶剂中进行,所述的有机溶剂为苯、四氯化碳、石油醚、四氢呋喃、二甲基甲酰胺、乙醚、二氯甲烷、三氯甲烷、甲苯、二甲苯、环己烷、正己烷、正庚烷、二氧六环、乙腈中的任意一种,优选为二甲基甲酰胺。所述有机溶剂的体积用量以式(4)所示的化合物的物质的量用量计为2~20mL/mmol。
作为进一步地改进,反应温度为0℃至150℃,优选加热至回流进行反应,反应时间为1小时到48小时。
作为进一步地改进,式(4)所示的化合物、式(5)所示的咪唑啉类化合物、过渡金属无机盐、有机膦配体,有机碱、一价铜盐的物质的量之比为1:0.95-5:0.01-1:0.02-2:1-10:1-10,优选为1:1-3:0.1-0.2:0.1-0.3:1.5-4:1-2。
所述偶联反应在氮气保护下进行,本反应要求严格无水无氧,因此在反应加料时在固体原料全部加完时抽气至真空,再充入高纯氮气,循环操作3次,然后在加入液体原料和溶剂以完全除去空气,补上氮气后再在氮气保护下进行反应。
所述反应结束后,反应液后处理制得式(1)所示的含手性亚胺喹啉咪唑啉类化合物,所述后处理方法为:反应液降到室温,加入乙醚溶液稀释,然后加入10%的稀氨水洗涤,干燥、浓缩再经柱层析分离,制得式(1)所示的手性含亚胺喹啉咪唑啉类化合物。柱层析所用洗脱剂为石油醚、乙酸乙酯混合溶剂。
所述式(4)所示的化合物可按照专利CN112851479A、CN113880822A公开的方法进行制备,具体的,可将式(2)所示的2-酰基-8-溴喹啉类化合物与式(3)所示的胺类化合物在催化剂的作用下进行缩合反应,制得式(4)所示的化合物;
R1-NH2 (3)
本发明还公开了一种手性含亚胺喹啉咪唑啉类化合物的金属络合物,所述金属络合物是由式(1)所示的手性含亚胺喹啉咪唑啉类化合物与过渡金属盐MEn络合反应制得,手性含亚胺喹啉咪唑啉类化合物的金属络合物的通式如下式(6)所示:
式(6)中,R1-R11、*如前所述;
式(6)中,M为过渡金属Fe、Co、Ni、Cu、Ag、Au、Ru、Rh、Pd、Os或Ir,优选为Fe;
Ε为卤化物(F、Cl、Br、I);拟卤化物(氰化物、氰酸根、四氟硼酸根、异氰酸根);羧酸、磺酸、膦酸的阴离子(碳酸根、甲酸根、乙酸根、丙酸根、甲基磺酸根、三氯甲基磺酸根、苯基磺酸根、甲苯磺酸根、磷酸根)中的任意一种;优选E为Cl;
n为E的个数,为1、2或3。
更进一步,优选所述手性含亚胺喹啉咪唑啉类化合物的金属络合物为以下之一:
所述手性含亚胺喹啉咪唑啉类化合物的金属络合物通过以下方法制得:
氮气保护下,式(1)所示的手性含亚胺喹啉咪唑啉类化合物和过渡金属盐MEn在有机溶剂中反应1~10小时,制得式(6)所示的手性含亚胺喹啉咪唑啉类化合物的金属络合物;所述有机溶剂为四氢呋喃或2-甲基四氢呋喃。
所述式(1)所示的手性含亚胺喹啉咪唑啉类化合物和过渡金属盐MEn的物质的量之比为0.9~2.2:1,优选0.9~1.1:1,更优选1~1.1:1。
手性含亚胺喹啉咪唑啉类化合物的金属络合物的合成可以在低的或高的温度下进行,例如-20~100℃温度,优选常温下进行即可。
反应结束后,所得反应液后处理制得式(6)所示的手性含亚胺喹啉咪唑啉类化合物的金属络合物,所述反应液后处理的方法一般为:反应液旋干,加入少量乙醚洗涤,抽滤,干燥,制得式(6)所示的手性含亚胺喹啉咪唑啉类化合物的金属络合物。
本发明还提供式(6)所示的手性含亚胺喹啉咪唑啉类化合物的金属络合物作为催化剂的应用。
金属络合物优选使用量为0.001-10mol%,更优选0.1-5mol%。
更具体的,所述催化是在催化剂存在下,在有机化合物的碳碳双键上进行氢化反应,反应在催化量的至少一种金属络合物式(6)存在下进行。
进一步,所述手性含亚胺喹啉咪唑啉类化合物的金属络合物可用于催化1,1-二烷基烯烃类化合物的不对称氢化反应制备手性或非手性的烷烃化合物。特别的,用本申请的金属络合物催化的手性产物的对映选择性很高,具有较大的应用价值。优选手性含亚胺喹啉咪唑啉类化合物的金属络合物用于催化烷基烯烃类化合物进行氢化反应生成手性烷烃化合物的反应。
更进一步,所述手性含亚胺喹啉咪唑啉类化合物的金属络合物可用于催化1,1-二烷基烯烃类化合物的氢化反应,反应式如式(i)所示。
Ra=Rb产物没有手性
Ra≠Rb产物具有手性
具体的,式(i)的氢化反应按以下方法进行:氮气保护下,式(6)所示的手性含亚胺喹啉咪唑啉类化合物的金属络合物、式(A)所示的1,1-二烷基烯烃化合物、十八烷基硅烷、乙腈和三乙基硼氢化钠在有机溶剂A中搅拌均匀,在反应体系中充入氢气,室温下搅拌反应12~24h,所得反应液通过硅胶短柱过滤,滤液蒸除溶剂得到式(B)所示的烷烃化合物。所述式(A)所示的1,1-二烷基烯烃化合物、三乙基硼氢化钠、十八烷基硅烷、乙腈、式(6)所示的手性含亚胺喹啉咪唑啉类化合物的物质的量之比为1:0.01~0.2:0.01~0.3:0.01~0.3:0.01~0.1,优选为1:0.1~0.2:0.15~0.2:0.15~0.2:0.01~0.1。所述有机溶剂A可以为甲苯。所述有机溶剂A的体积用量以式(A)所示的1,1-二烷基烯烃化合物的物质的量计为1~20mL/mmol。
所述化学式(i)中,反应原料式(A)为1,1-二烷基烷基烯烃化合物,Ra、Rb各自独立为C1~C10的烷基,所述烷基上的H不被取代或者被一个以上的取代基C取代,所述的取代基C为C1-C4烷氧基、苯基或萘基;所述苯基或萘基上的H不被取代或被一个以上的取代基D取代,所述的取代基D为C1-C4烷基、C1-C4烷氧基、C1-C4硅烷基或卤素。
Ra、Rb可以相同也可以不同,Ra、Rb不同时,得到的式(B)为手性烷烃化合物
进一步,优选所述手性含亚胺喹啉咪唑啉类化合物的金属络合物用于催化2-异丙基-4-(4-甲氧基苯基)-1-丁烯的氢化反应
本发明的有益效果如下:
本发明提供了一种新型手性含亚胺喹啉咪唑啉类化合物。
本发明提供了一种新型手性含亚胺喹啉咪唑啉类化合物可以与过渡金属Fe、Co、Ni、Cu、Ag、Au、Ru、Rh、Pd、Os、Ir形成稳定的金属络合物。
本发明还提供所述手性含亚胺喹啉咪唑啉类化合物的金属络合物作为均相催化剂的用途,催化剂通过对烷基烯烃的催化氢化可以用于制备手性或非手性的烷基化合物,特别可用于制备高区域选择性和光学选择性的手性产物,手性产物的对映选择性可达85%以上。
本发明金属络合物催化剂制备的手性或非手性有机化合物是活性物质或用于制备该物质的中间物,特别是可用于香料和增香剂、药物制剂、农用化学品的生产方面。
具体实施方式
下面通过具体实施例对本发明的技术方案作进一步地详细说明:
以下实施例解释本发明。所有反应在无空气的氮气和脱气的溶剂中进行。但并不限制本发明内容。
实施例中,式(3-A)所示的胺类化合物是市售可得的,式(2-A)所示的2-酰基-8-溴喹啉类化合物依照文献(K.E.Pump,A.E.Pazio,K./>L.Cavallo,C.Slugovc,BeilsteinJ.Org.Chem.2015,11,1458.)制备。式(4-A)示的各种亚胺依照专利(CN112851479A、CN113880822A)制备。式(5-A)所示的咪唑啉类化合物依照文献(J.Guo,B.Cheng,X.Shen,Z.LuJ.Am.Chem.Soc.2017,139,15316–15319)制备。
8-溴-2-亚胺喹啉(4-A1)的制备(E)-1-(8-溴喹啉-2-基)-N-(2,6-二甲基苯基)乙烷-1-亚胺
2,6-二甲基苯胺(2.7924g,23mmol,1.2equiv)与8-溴-2-乙酰基喹啉(4.7916g,19mmol,1.0equiv)溶于48mL甲苯中,对甲苯磺酸(0.0738g,0.38mmol,2mol%)催化,加热至回流,分水器分水,反应24h,反应完毕后,降至室温,过滤,浓缩后-20℃下乙醇重结晶得到黄色固体4.5437g(12.9mmol,67%),记为8-溴-2-亚胺喹啉(4-A1)。
IR(neat):2970,2916,1644,1366,1091,760cm-1
1H NMR(400MHz,CDCl3)δ8.60(d,J=8.4Hz,1H),8.23(d,J=8.4Hz,1H),8.09(d,J=7.6Hz,1H),7.85(d,J=8.0Hz,1H),7.45(dd,J=7.6,8.0Hz,1H),7.10(d,J=7.6Hz,2H),6.96(dd,J=7.6,7.6Hz,1H),2.40(s,3H),2.05(s,6H).13C NMR(100MHz,CDCl3)δ167.6,156.5,148.8,144.3,136.7,133.2,130.0,127.9,127.8,127.4,125.9,125.2,123.2,119.4,17.9,16.3.
HRMS(ESI)calculated for[C19H18BrN2]+requires m/z 353.0648,found m/z353.0663
8-溴-2-亚胺喹啉(4-A2)的制备(E)-1-(8-溴喹啉-2-基)-N-(2,6-二异丙基苯基)乙烷-1-亚胺
2,6-二异丙基苯胺(4.2552g,24mmol,1.2equiv)与8-溴-2-乙酰基喹啉(5.0007g,20mmol,1.0equiv)溶于50mL甲苯中,对甲苯磺酸(0.0760g,0.4mmol,2mol%)催化,加热至回流,分水器分水,反应24h,反应完毕后,降至室温,过滤,浓缩后-20℃下乙醇重结晶得到黄色固体7.3078g(18mmol,90%),记为8-溴-2-亚胺喹啉(4-A2)。
IR(neat):2959,2924,1643,1493,1362,760cm-1
1H NMR(400MHz,CDCl3)δ8.59(d,J=8.8Hz,1H),8.23(d,J=8.4Hz,1H),8.09(dd,J=1.2,7.6Hz,1H),7.84(dd,J=1.2,8.0Hz,1H),2.49-2.30(m,7H),1.14(t,J=7.6Hz,3H);
13C NMR(100MHz,CDCl3)δ167.3,156.5,146.5,144.3,136.6,135.5,133.1,130.0,127.8,127.4,125.9,123.7,123.0,119.4,28.3,23.2,22.8,16.9;
HRMS(ESI)calculated for[C23H26BrN2]+requires m/z 409.1274,found m/z409.1290.
将2,6-二甲基苯胺改为2,6-二乙基苯胺,制得(E)-1-(8-溴喹啉-2-基)-N-(2,6-二乙基苯基)乙烷-1-亚胺,记为8-溴-2-亚胺喹啉(4-A3)
将2,6-二甲基苯胺改为2,6-二异丙基-4-甲氧基苯胺,制得(E)-1-(8-溴喹啉-2-基)-N-(2,6-二异丙基-4-甲氧基苯基)乙烷-1-亚胺,记为8-溴-2-亚胺喹啉(4-A4)
将2,6-二甲基苯胺改为2,4,6-三叔丁基苯胺,制得(E)-1-(8-溴喹啉-2-基)-N-(2,4,6-三叔丁基苯基)乙烷-1-亚胺,记为8-溴-2-亚胺喹啉(4-A5)
实施例1含亚胺喹啉咪唑啉化合物L的制备
(S,E)-1-(8-(4-(tert-butyl)-1-phenyl-4,5-dihydro-1H-imidazol-2-yl)quinolin-2-yl)-N-(2,6-diisopropylphenyl)ethan-1-imine(La).氮气保护条件下,在50mL的史莱克反应管里加入(E)-1-(8-溴喹啉-2-基)-N-(2,6-二异丙基苯基)乙烷-1-亚胺(8-溴-2-亚胺喹啉(4-A2))(0.8230g,2.0mmol),Pd(OAc)2(0.0450g,0.20mmol),PPh3(0.1053g,0.40mmol),CuI(0.5732g,3.0mmol),DBU(0.5mL,1.02g/mL,3.0mmol)和叔丁基N-苯基咪唑啉环(0.3853g,1.9mmol),DMF(12mL),110℃条件下回流搅拌48小时,恢复到室温后,加入10%稀氨水溶液洗涤三次,加入无水硫酸钠干燥,减压旋蒸去除溶剂,通过柱层析(洗脱剂PE/EA=5/1)分离得到0.4721g La,为黄色油状产物(0.89mmol,47%yield).Optical Rotation:[α]20 D=+2.4(c 0.735,CHCl3).IR(neat):3061,2960,2868,2198,1599,1500cm-1;1H NMR:(400MHz,CHCl3)δ8.34(d,J=8.8Hz,1H),8.13(d,J=8.8Hz,1H),8.06(d,J=7.3Hz,1H),7.91(d,J=7.9Hz,1H),7.65(t,J=8.2Hz,1H),7.15(d,J=7.6Hz,1H),7.10-7.06(m,1H),6.85(dd,J=7.9,7.9Hz,2H),6.67(t,J=7.2Hz,1H),6.58(d,J=7.9Hz,2H),4.13-4.00(m,3H),2.60-2.57(m,2H),2.08(s,3H),1.12-1.07(m,21H);13C NMR:(100MHz,CDCl3)δ167.2,160.2,155.5,146.4,144.7,141.3,135.8,135.5,135.4,133.0,130.7,129.3,128.3,128.0,127.1,123.5,122.85,122.82,121.4,118.6,118.4,52.2,28.09,28.05,26.1,23.0,22.8,17.0;HRMS(ESI)calculated for[C36H43N4]+(M+H+),requires m/z 531.3482,found m/z 531.3484.
(S,E)-1-(8-(1,4-diisopropyl-4,5-dihydro-1H-imidazol-2-yl)quinolin-2-yl)-N-(2,6-diisopropylphenyl)ethan-1-imine(Lb).氮气保护条件下,在50mL的史莱克反应管里加入(E)-1-(8-溴喹啉-2-基)-N-(2,6-二异丙基苯基)乙烷-1-亚胺(0.8190g,2.0mmol),Pd(OAc)2(0.0450g,0.20mmol),PPh3(0.1050g,0.40mmol),CuI(0.5743g,3.0mmol),DBU(0.5mL,1.02g/mL,3.0mmol)和异丙基N-异丙基咪唑啉环(0.3853g,1.9mmol),DMF(12mL),110℃条件下回流搅拌48小时,恢复到室温后,加入10%稀氨水溶液洗涤三次,加入无水硫酸钠干燥,减压旋蒸去除溶剂,通过柱层析(洗脱剂PE/EA=5/1)分离得到0.3328g Lb,为黄色油状产物(0.69mmol,39%yield).Optical Rotation:[α]20 D=-20.1(c 0.530,CHCl3).IR(neat):2962,2870,2174,1597,1462,1364;1H NMR:(400MHz,CDCl3)δ8.52(d,J=9.1Hz,1H),8.28(d,J=8.27Hz,1H),7.95(d,J=8.2Hz,1H),7.86(d,J=7.3Hz,1H),7.65(t,J=7.3Hz,1H),7.22(d,J=7.3Hz,2H),7.15(t,J=8.2Hz,1H),4.14-4.08(m,1H),3.61(t,J=10.6Hz,1H),3.41-3.34(m,2H),2.83-2.75(m,2H),2.32(s,3H),2.01-1.93(m,1H),1.20-1.16(m,12H),1.11-1.06(m,12H);13C NMR:(100MHz,CHCl3)δ167.8,163.8,156.3,146.5,145.1,136.3,135.6,135.62,130.56,129.0,128.5,128.4,128.3,127.0,123.6,122.98,122.95,119.1,69.9,46.3,33.2,28.2,23.2,22.84,22.81,20.7,20.0,18.9,18.1,17.2;HRMS(ESI)calculated for[C32H43N4]+(M+H+),requires m/z483.3482,found m/z 483.3480.
(S,E)-1-(8-(1-benzyl-4-cyclohexyl-4,5-dihydro-1H-imidazol-2-yl)quinolin-2-yl)-N-(2,6-diisopropylphenyl)ethan-1-imine(Lc).氮气保护条件下,在50mL的史莱克反应管里加入(E)-1-(8-溴喹啉-2-基)-N-(2,6-二异丙基苯基)乙烷-1-亚胺(1.2226g,3.0mmol),Pd(OAc)2(0.0697g,0.30mmol),PPh3(0.1696g,0.60mmol),CuI(0.5771g,3.0mmol),DBU(0.7061g,4.5mmol)和环己基N-苄基咪唑啉环(0.7264g,3.0mmol),DMF(12mL),110℃条件下回流搅拌48小时,恢复到室温后,加入10%稀氨水溶液洗涤三次,加入无水硫酸钠干燥,减压旋蒸去除溶剂,通过柱层析(洗脱剂PE/EA=5/1)分离得到1.2013g Lc,为黄色油状产物(2.11mmol,70%yield).Optical Rotation:[α]20 D=-13.6(c 1.445,CHCl3).IR(neat):2960,2923,2852,2182,1601,1455;1H NMR:(400MHz,CHCl3)δ8.55(d,J=8.7Hz,1H),8.24(d,J=8.7Hz,1H),7.92(d,J=7.4Hz,2H),7.63(1,J=7.4Hz,1H),7.25-7.19(m,5H),7.16-7.10(m,3H),4.15-3.94(m,3H),3.49(t,J=9.6Hz,1H),3.16(t,J=8.4Hz,1H),2.80-2.74(m,2H),2.36(s,3H),1.97(d,J=10.8Hz,1H),1.76-1.59(m,5H),1.22-1.14(m,17H);13C NMR:(100MHz,CHCl3)δ167.3,164.3,156.0,146.5,145.4,138.0,136.2,135.5,135.4,132.2,130.5,129.1,128.6,128.3,127.4,127.1,127.0,123.6,123.0,122.9,118.9,70.2,52.7,52.0,43.2,29.6,28.9,28.2,26.5,26.2,23.1,22.8,22.7,17.0;HRMS(ESI)calculated for[C39H47N4]+(M+H+),requires m/z571.3795,found m/z 571.3796.
(S,E)-N-(2,6-diisopropylphenyl)-1-(8-(4-ethyl-1-phenyl-4,5-dihydro-1H-imidazol-2-yl)quinolin-2-yl)ethan-1-imine(Ld).氮气保护条件下,在50mL的史莱克反应管里加入(E)-1-(8-溴喹啉-2-基)-N-(2,6-二异丙基苯基)乙烷-1-亚胺(1.2282g,3.0mmol),Pd(OAc)2(0.0694g,0.30mmol),PPh3(0.1638g,0.60mmol),CuI(0.5845g,3.0mmol),DBU(0.6785g,4.5mmol)和乙基N-苯基咪唑啉环(0.5088g,3.0mmol),DMF(12mL),110℃条件下回流搅拌48小时,恢复到室温后,加入10%稀氨水溶液洗涤三次,加入无水硫酸钠干燥,减压旋蒸去除溶剂,通过柱层析(洗脱剂PE/EA=5/1)分离得到1.2809g Ld,为黄色油状产物(2.55mmol,85%yield).Optical Rotation:[α]20 D=+18.5(c 0.545,CHCl3).IR(neat):3060,2961,2929,2870,2188,1598,1501;1H NMR:(400MHz,CHCl3)δ8.38(d,J=8.37Hz,1H),8.13(d,J=8.12Hz,1H),8.04(d,J=7.4Hz,1H),7.91(d,J=8.2Hz,1H),7.64(t,J=8.2Hz,1H),7.15(d,J=7.4Hz,2H),7.10-7.07(m,1H),6.85(t,J=6.6Hz,2H),6.67(t,J=7.4Hz,1H),6.56(d,J=7.4Hz,2H),4.30-4.17(m,2H),3.86(t,J=8.2Hz,1H),2.63-2.57(m,2H),2.10(s,3H),1.98-1.91(m,1H),1.80-1.73(m,1H),1.12-1.09(m,15H);13CNMR:(100MHz,CHCl3)δ167.1,160.2,155.4,146.5,144.7,141.3,135.9,135.5,135.5,132.8,130.6,129.4,128.4,128.1,127.1,123.5,122.9,121.3,118.6,118.1,65.4,56.0,29.1,28.1,28.1,23.1,22.8,22.8,16.9,10.2;HRMS(ESI)calculated for[C34H39N4]+(M+H+),requires m/z 503.3169,found m/z 503.3172.
(S,E)-1-(8-(1-benzyl-4-(tert-butyl)-4,5-dihydro-1H-imidazol-2-yl)quinolin-2-yl)-N-(2,6-dimethylphenyl)ethan-1-imine(Le).氮气保护条件下,在50mL的史莱克反应管里加入(E)-1-(8-溴喹啉-2-基)-N-(2,6-二甲基苯基)乙烷-1-亚胺(0.7062g,2.0mmol),Pd(OAc)2(0.0494g,0.20mmol),PPh3(0.1638g,0.40mmol),CuI(0.5845g,3.0mmol),DBU(0.6785g,4.5mmol)和叔丁基N-苯基咪唑啉环(0.5088g,3.0mmol),DMF(12mL),110℃条件下回流搅拌48小时,恢复到室温后,加入10%稀氨水溶液洗涤三次,加入无水硫酸钠干燥,减压旋蒸去除溶剂,通过柱层析(洗脱剂PE/EA=5/1)分离得到0.7675g Le,为黄色油状产物(1.62mmol,81%yield).Optical Rotation:[α]20 D=-8.3(c 0.565,CHCl3).IR(neat):3048,2956,2868,2201,1598,1501;1H NMR:(400MHz,CHCl3)δ8.33(d,J=9.3Hz,1H),8.13(d,J=9.3Hz,1H),8.06(d,J=6.2Hz,1H),7.91(d,J=7.90Hz,1H),7.65(t,J=8.2Hz,1H),7.31(t,J=8.2Hz,1H),7.05(d,J=7.2Hz,2H),6.84(t,J=7.2Hz,2H),6.66(t,J=9.3Hz,2H),6.58(d,J=8.2Hz,2H),4.13-3.97(m,3H),2.05(s,3H),1.94(s,6H),1.08(s,9H);13C NMR:(100MHz,CDCl3)δ167.2,160.2,155.5,146.4,144.7,141.3,135.8,135.5,135.4,133.0,130.7,129.3,128.3,128.0,127.1,123.5,122.85,122.82,121.4,118.6,118.4,52.2,28.09,28.05,26.1,23.0,22.8,17.0;HRMS(ESI)calculated for[C32H35N4]+(M+H+),requires m/z 475.2856,found m/z475.2855.
(E)-1-(8-((S)-1-benzyl-4-((S)-sec-butyl)-4,5-dihydro-1H-imidazol-2-yl)quinolin-2-yl)-N-(2,6-dimethylphenyl)ethan-1-imine(Lf).氮气保护条件下,在50mL的史莱克反应管里加入(E)-1-(8-溴喹啉-2-基)-N-(2,6-二甲基苯基)乙烷-1-亚胺(0.7050g,2.0mmol),Pd(OAc)2(0.0450g,0.20mmol),PPh3(0.1101g,0.40mmol),CuI(0.5690g,3.0mmol),DBU(0.5mL,1.02g/mL,3.0mmol)和仲丁基N-苄基咪唑啉环(0.5088g,3.0mmol),DMF(12mL),110℃条件下回流搅拌48小时,恢复到室温后,加入10%稀氨水溶液洗涤三次,加入无水硫酸钠干燥,减压旋蒸去除溶剂,通过柱层析(洗脱剂PE/EA=5/1)分离得到0.4278g Lf,为黄色油状产物(0.88mmol,46%yield).Optical Rotation:[α]20 D=-1.5(c 0.530,CHCl3).IR(neat):2960,2873,2178,1645,1595,1204;1H NMR:(400MHz,CHCl3)δ8.55(d,J=8.7Hz,1H),8.25(d,J=8.7Hz,1H),7.94-7.91(m,2H),7.63(t,J=7.62Hz,1H),7.24-7.21(m,3H),7.16(d,J=7.4Hz,2H),7.10(d,J=7.4Hz,2H),6.97(t,J=7.4Hz,1H),4.19-3.93(m,3H),3.47(s,J=3.44Hz,1H),3.14(t,J=9.9Hz,1H),2.32(s,J=3Hz,3H),2.08-2.04(m,6H),1.67-1.60(m,1H),1.28-1.21(m,1H),0.96-0.90(m,6H);13CNMR:(100MHz,CHCl3)δ167.5,164.3,156.0,148.7,145.3,137.9,136.2,132.1,130.5,129.1,128.5,128.4,128.3,128.3,127.8,127.8,127.4,127.1,127.0,125.1,125.0,123.0,118.9,77.3,77.0,76.7,69.4,51.9,51.8,39.4,26.1,17.9,17.8,16.4,14.5,11.6;HRMS(ESI)calculated for[C33H37N4]+(M+H+),requires m/z 489.3013,found m/z489.3013.
(E)-1-(8-((S)-1-benzyl-4-((S)-sec-butyl)-4,5-dihydro-1H-imidazol-2-yl)quinolin-2-yl)-N-(2,6-diethylphenyl)ethan-1-imine(Lg).氮气保护条件下,在50mL的史莱克反应管里加入(E)-1-(8-溴喹啉-2-基)-N-(2,6-二乙基苯基)乙烷-1-亚胺(0.3909g,1.0mmol),Pd(OAc)2(0.0235g,0.10mmol),PPh3(0.0548g,0.20mmol),CuI(0.2055g,1.0mmol),DBU(0.25mL,1.02g/mL,1.5mmol)和仲丁基N-苄基咪唑啉环(0.2250g,1.0mmol),DMF(12mL),110℃条件下回流搅拌48小时,恢复到室温后,加入10%稀氨水溶液洗涤三次,加入无水硫酸钠干燥,减压旋蒸去除溶剂,通过柱层析(洗脱剂PE/EA=5/1)分离得到0.0256g Lg,为黄色油状产物(0.050mmol,5.0%yield).Optical Rotation:[α]20 D=-3.9(c 1.045,CHCl3).IR(neat):2963,2928,2873,2186,1593,1455;1H NMR:(400MHz,CHCl3)δ8.58(d,J=8.9Hz,1H),8.30(d,J=8.29Hz,1H),8.10(d,J=8.09Hz,1H),8.03(d,J=8.02Hz,1H),7.73(t,J=7.5Hz,1H),7.29-7.26(m,3H),7.16-7.05(m,5H),4.34-4.28(m,1H),4.22(d,J=15.2Hz,1H),4.09(d,J=15.2Hz,1H),3.63(t,J=10.2Hz,1H),3.32(t,J=9.2Hz,1H),2.46-2.33(m,4H),2.30(s,3H),1.58-1.52(m,1H),1.25-1.21(m,1H),1.19-1.13(m,6H),0.97(d,J=6.5Hz,3H),0.91(t,J=7.3Hz,3H);13C NMR:(100MHz,CHCl3)δ166.8,164.8,156.6,147.6,144.8,136.7,131.5,130.9,130.8,128.7,128.7,127.9,127.7,127.3,126.0,125.9,123.5,119.5,77.3,77.2,77.0,76.7,51.8,51.1,38.7,25.7,24.6,24.6,16.8,14.0,13.7,13.7,11.5,-0.0;HRMS(ESI)calculated for[C35H41N4]+(M+H+),requires m/z 517.3326,found m/z 517.3329.
(S,E)-1-(8-(1-benzyl-4-cyclohexyl-4,5-dihydro-1H-imidazol-2-yl)quinolin-2-yl)-N-(2,6-diethylphenyl)ethan-1-imine(Lh).氮气保护条件下,在50mL的史莱克反应管里加入(E)-1-(8-溴喹啉-2-基)-N-(2,6-二乙基苯基)乙烷-1-亚胺(0.3912g,1.0mmol),Pd(OAc)2(0.0239g,0.10mmol),PPh3(0.0562g,0.20mmol),CuI(0.1950g,1.0mmol),DBU(0.2839g,1.5mmol)和环己基N-苄基咪唑啉环(0.2357g,1.0mmol),DMF(12mL),110℃条件下回流搅拌48小时,恢复到室温后,加入10%稀氨水溶液洗涤三次,加入无水硫酸钠干燥,减压旋蒸去除溶剂,通过柱层析(洗脱剂PE/EA=5/1)分离得到0.0806g Lh,为黄色油状产物(0.15mmol,15%yield).Optical Rotation:[α]20 D=-13.5(c 1.250,CHCl3).IR(neat):2924,2852,2184,1597,1452,1100;1H NMR:(400MHz,CHCl3)δ8.57(d,J=8.5Hz,1H),8.27(d,J=8.27Hz,1H),8.06(d,J=7.0Hz,1H),7.99(d,J=7.8Hz,1H),7.71(t,J=7.8Hz,1H),7.25-7.21(m,3H),7.16-7.12(m,4H),7.07(t,J=9.3Hz,1H),4.18(d,J=14.7Hz,1H),4.05-4.00(m,2H),3.58(t,J=9.4Hz,1H),3.25(t,J=9.4Hz,1H),2.46-2.35(m,4H),2.32(s,3H),1.87(d,J=12.1Hz,1H),1.70-1.55(m,5H),1.19-1.02(m,11H);13C NMR:(100MHz,CHCl3)δ167.0,164.6,156.3,147.7,145.0,136.5,131.2,130.9,130.8,129.9,128.6,128.5,127.6,127.5,127.3,126.0,125.9,123.4,119.2,77.3,77.0,76.7,52.3,51.8,42.8,29.2,28.5,26.4,26.0,26.0,24.6,24.6,16.7,13.7,13.7;HRMS(ESI)calculated for[C37H43N4]+(M+H+),requires m/z 543.3482,found m/z 543.3485.
(S,E)-N-(2,6-diethylphenyl)-1-(8-(4-ethyl-1-phenyl-4,5-dihydro-1H-imidazol-2-yl)quinolin-2-yl)ethan-1-imine(Li).氮气保护条件下,在50mL的史莱克反应管里加入(E)-1-(8-溴喹啉-2-基)-N-(2,6-二乙基苯基)乙烷-1-亚胺(1.1435g,3.0mmol),Pd(OAc)2(0.0690g,0.30mmol),PPh3(0.1652g,0.60mmol),CuI(0.5791g,3.0mmol),DBU(0.7183g,4.5mmol)和乙基N-苯基咪唑啉环(0.5360g,3.0mmol),DMF(12mL),110℃条件下回流搅拌48小时,恢复到室温后,加入10%稀氨水溶液洗涤三次,加入无水硫酸钠干燥,减压旋蒸去除溶剂,通过柱层析(洗脱剂PE/EA=5/1)分离得到1.2725g Li,为黄色油状产物(2.683mmol,89%yield).Optical Rotation:[α]20 D=+9.7(c 1.180,CHCl3).IR(neat):2965,2930,2872,2192,1597,1458;1H NMR:(400MHz,CHCl3)δ8.35(d,J=8.2Hz,1H),8.14(d,J=9.6Hz,1H),8.04(d,J=7.4Hz,1H),7.92(d,J=7.4Hz,1H),7.65(t,J=7.4Hz,1H),7.09(d,J=7.4Hz,2H),7.02(t,J=7.4Hz,1H),6.85(t,J=8.2Hz,2H),6.67(t,J=6.7Hz,1H),6.56(d,J=8.2Hz,2H),4.30-4.12(m,2H),3.86(t,J=8.2Hz,1H),2.31-2.21(m,4H),2.07(s,3H),1.98-1.91(m,1H),1.80-1.73(m,1H),1.12-1.05(m,9H);13C NMR:(100MHz,CHCl3)δ167.1,160.2,155.4,147.8,144.7,141.4,135.9,132.8,131.0,130.9,130.6,129.4,128.4,128.1,127.1,125.9,125.8,123.3,121.4,118.6,118.2,77.3,77.2,77.0,76.7,65.4,56.0,29.1,24.5,24.5,16.6,13.6,10.2;HRMS(ESI)calculated for[C37H43N4]+(M+H+),requires m/z 475.2856,found m/z 475.2854.
(E)-1-(8-((S)-4-((S)-sec-butyl)-1-phenyl-4,5-dihydro-1H-imidazol-2-yl)quinolin-2-yl)-N-(2,6-diethylphenyl)ethan-1-imine(LJ).氮气保护条件下,在50mL的史莱克反应管里加入(E)-1-(8-溴喹啉-2-基)-N-(2,6-二乙基苯基)乙烷-1-亚胺(1.1571g,3.0mmol),Pd(OAc)2(0.0684g,0.30mmol),PPh3(0.1665g,0.60mmol),CuI(0.5748g,3.0mmol),DBU(0.7252g,4.5mmol)和仲丁基N-苯基咪唑啉环(0.6084g,3.0mmol),DMF(12mL),110℃条件下回流搅拌48小时,恢复到室温后,加入10%稀氨水溶液洗涤三次,加入无水硫酸钠干燥,减压旋蒸去除溶剂,通过柱层析(洗脱剂PE/EA=5/1)分离得到0.5006g Lj,为黄色油状产物(1.0mmol,33%yield).Optical Rotation:[α]20 D=-3.8(c 0.995,CHCl3).IR(neat):2961,2871,2192,1597,1500,1469;1H NMR:(400MHz,CHCl3)δ8.36(d,J=8.4Hz,1H),8.14(d,J=8.4Hz,1H),8.01(d,J=7.1Hz,1H),7.92(d,J=8.4Hz,1H),7.64(t,J=7.8Hz,1H),7.10(d,J=7.8Hz,2H),7.02(t,J=8.4Hz,1H),6.85(t,J=7.8Hz,2H),6.67(t,J=7.1Hz,1H),6.55(d,J=8.4Hz,2H),4.42-4.34(m,1H),4.24-4.19(m,1H),3.79(t,J=8.7Hz,1H),2.32-2.22(m,4H),2.08(s,3H),1.99-1.85(m,2H),1.57-1.50(m,1H),1.07(t,J=7.5Hz,6H),1.03-0.98(m,6H);13C NMR:(100MHz,CHCl3)δ167.0,159.9,155.3,147.7,144.6,141.3,135.8,132.6,130.8,130.8,130.5,129.3,128.2,128.0,126.9,125.8,125.7,123.1,121.2,118.5,117.9,77.3,77.3,77.0,76.9,76.7,76.6,62.2,56.9,46.0,46.0,25.1,24.4,24.4,22.8,22.7,16.5,13.5;HRMS(ESI)calculated for[C34H39N4]+(M+H+),requires m/z 503.3169,found m/z 503.3171.
(S,E)-N-(2,6-diisopropyl-4-methoxyphenyl)-1-(8-(4-isopropyl-1-phenyl-4,5-dihydro-1H-imidazol-2-yl)quinolin-2-yl)ethan-1-imine(Lk).氮气保护条件下,在50mL的史莱克反应管里加入(E)-1-(8-溴喹啉-2-基)-N-(2,6-二异丙基-4-甲氧基苯基)乙烷-1-亚胺(1.3095g,3.0mmol),Pd(OAc)2(0.0780g,0.30mmol),PPh3(0.1644g,0.60mmol),CuI(0.5738g,3.0mmol),DBU(0.6940g,4.5mmol)和异丙基N-苯基咪唑啉环(0.5740g,3.0mmol),DMF(12mL),110℃条件下回流搅拌48小时,恢复到室温后,加入10%稀氨水溶液洗涤三次,加入无水硫酸钠干燥,减压旋蒸去除溶剂,通过柱层析(洗脱剂PE/EA=5/1)分离得到1.2228g Lk,为黄色油状产物(2.2mmol,75%yield).Optical Rotation:[α]20 D=-0.5(c 1.250,CHCl3).IR(neat):2961,2871,2192,1599,1462,1202;1H NMR:(400MHz,CDCl3)δ8.38(d,J=8.6Hz,1H),8.16(d,J=8.6Hz,1H),8.08(d,J=6.8Hz,1H),7.95(d,J=7.8Hz,1H),7.68(t,J=7.3Hz,1H),6.88(t,J=8.2Hz,2H),6.75(s,2H),6.70(t,J=7.7Hz,1H),6.60(d,J=7.7Hz,2H),4.24-4.01(m,2H),3.99-3.95(m,1H),3.87(s,3H),2.68-2.59(m,2H),2.10(s,3H),1.17-1.09(m,18H);13C NMR:(100MHz,CDCl3)δ168.1,160.2,156.1,155.6,144.7,141.3,140.0,137.0,136.9,135.8,132.8,130.6,129.4,128.3,128.0,127.0,121.3,118.6,118.2,108.4,108.4,77.3,77.0,76.7,69.9,55.2,53.5,32.9,28.3,28.2,23.0,23.0,22.8,22.7,19.1,18.1,16.8;HRMS(ESI)calculated for[C36H43N4O]+(M+H+),requires m/z 547.3431,found m/z 547.3432.
(S,E)-N-(2,6-diisopropylphenyl)-1-(8-(4-isopropyl-1-phenyl-4,5-dihydro-1H-imidazol-2-yl)quinolin-2-yl)ethan-1-imine(Ll).氮气保护条件下,在50mL的史莱克反应管里加入(E)-1-(8-溴喹啉-2-基)-N-(2,6-二异丙基苯基)乙烷-1-亚胺(1.3095g,3.0mmol),Pd(OAc)2(0.0780g,0.30mmol),PPh3(0.1644g,0.60mmol),CuI(0.5738g,3.0mmol),DBU(0.6940g,4.5mmol)和异丙基N-苯基咪唑啉环(0.5740g,3.0mmol),DMF(12mL),110℃条件下回流搅拌48小时,恢复到室温后,加入10%稀氨水溶液洗涤三次,加入无水硫酸钠干燥,减压旋蒸去除溶剂,通过柱层析(洗脱剂PE/EA=5/1)分离得到1.0323g Ll,为黄色油状产物(2.0mmol,67%yield).Optical Rotation:[α]20 D=14.8(c 1.095,CHCl3).IR(neat):2961,2870,1599,1500,1462,1384;1H NMR:(400MHz,CDCl3)δ8.36(d,J=8.5Hz,1H),8.14(d,J=8.5Hz,1H),8.06(d,J=6.7Hz,1H),7.93(d,J=8.0Hz,1H),7.65(t,J=7.5Hz,1H),7.15(d,J=7.6Hz,2H),7.08(t,J=7.2Hz,1H),6.85(t,J=8.0Hz,2H),6.68(t,J=6.7Hz,1H),6.58(d,J=7.2Hz,2H),4.21-4.10(m,2H),3.97-3.91(m,1H),2.63-2.57(m,2H),2.08(s,4H),1.14-1.06(m,18H);13C NMR:(100MHz,CDCl3)δ167.1,160.2,155.4,146.4,144.6,141.3,135.8,135.5,135.4,132.8,130.6,129.4,128.3,128.0,127.0,123.5,122.8,122.8,121.3,118.6,118.2,53.4,32.9,28.1,28.0,23.0,22.8,22.8,19.1,18.1,16.9;HRMS(ESI)calculated for[C36H43N4O]+(M+H+),requires m/z 517.3326,found m/z 517.3326.
(S,E)-1-(8-(4-(tert-butyl)-1-phenyl-4,5-dihydro-1H-imidazol-2-yl)quinolin-2-yl)-N-(2,6-diethylphenyl)ethan-1-imine(Lm).氮气保护条件下,在50mL的史莱克反应管里加入(E)-1-(8-溴喹啉-2-基)-N-(2,6-二乙基苯基)乙烷-1-亚胺(1.1585g,3.0mmol),Pd(OAc)2(0.0679g,0.30mmol),PPh3(0.1579g,0.60mmol),CuI(0.5712g,3.0mmol),DBU(0.7138g,4.5mmol)和叔丁基N-苯基咪唑啉环(0.8568g,4.2mmol),DMF(12mL),110℃条件下回流搅拌48小时,恢复到室温后,加入10%稀氨水溶液洗涤三次,加入无水硫酸钠干燥,减压旋蒸去除溶剂,通过柱层析(洗脱剂PE/EA=5/1)分离得到0.8568g Lm,为黄色油状产物(1.8mmol,59%yield).Optical Rotation:[α]20 D=9.8(c 1.030,CHCl3).IR(neat):2959,2869,2194,1598,1500,1475;1H NMR:(400MHz,CHCl3)δ8.33(d,J=8.5Hz,1H),8.12(d,J=8.5Hz,1H),8.05(d,J=7.3Hz,1H),7.91(d,J=8.5Hz,1H),7.65(t,J=7.8Hz,1H),7.09(d,J=7.8Hz,2H),7.01(t,J=7.5Hz,1H),6.84(t,J=8.2Hz,2H),6.67(t,J=6.9Hz,1H),6.57(d,J=7.8Hz,2H),4.13-4.00(m,3H),2.28-2.23(m,4H),3.0(s,3H),1.09-1.05(m,15H);HRMS(ESI)calculated for[C34H39N4]+(M+H+),requires m/z 503.3169,found m/z 503.3171.
(S,E)-1-(8-(4-isopropyl-1-phenyl-4,5-dihydro-1H-imidazol-2-yl)quinolin-2-yl)-N-(2,4,6-tri-tert-butylphenyl)methanimine(Ln).氮气保护条件下,在50mL的史莱克反应管里加入(E)-1-(8-溴喹啉-2-基)-N-(2,4,6-三叔丁基苯基)乙烷-1-亚胺(1.4760g,3.0mmol),Pd(OAc)2(0.0694g,0.30mmol),PPh3(0.1611g,0.60mmol),CuI(0.5760g,3.0mmol),DBU(0.9165g,6.0mmol)和异丙基N-苯基咪唑啉环(0.5651g,3.0mmol),DMF(12mL),110℃条件下回流搅拌48小时,恢复到室温后,加入10%稀氨水溶液洗涤三次,加入无水硫酸钠干燥,减压旋蒸去除溶剂,通过柱层析(洗脱剂PE/EA=5/1)分离得到1.3209g Lm,为黄色油状产物(2.2mmol,75%yield).Optical Rotation:[α]20 D=-7.5(c 1.095,CHCl3).IR(neat):2957,2925,2870,1597,1500,1475;1H NMR:(400MHz,CHCl3)δ8.24(d,J=8.7Hz,1H),8.18(d,J=8.7Hz,1H),8.12(s,1H),8.04(d,J=6.9Hz,1H),7.91(d,J=8.1Hz,1H),7.64(t,J=7.7Hz,1H),7.37(s,2H),6.80(t,J=7.9Hz,2H),6.64(t,J=7.9Hz,1H),6.57(d,J=7.9Hz,2H),4.18-4.12(m,1H),4.06-3.96(m,1H),3.92-3.84(m,1H),2.05-1.96(m,1H),1.37(s,9H),1.24(s,18H),1.08(d,J=6.7Hz,3H),1.02(d,J=6.7Hz,3H);HRMS(ESI)calculated for[C40H51N4]+(M+H+),requires m/z 587.4108,found m/z 587.4109.
(S,E)-N-(2,6-dimethylphenyl)-1-(8-(4-isopropyl-1-(m-tolyl)-4,5-dihydro-1H-imida zol-2-yl)quinolin-2-yl)ethan-1-imine(Lo).氮气保护条件下,在50mL的史莱克反应管里加入(E)-1-(8-溴喹啉-2-基)-N-(2,6-二甲基苯基)乙烷-1-亚胺(1.0594g,3.0mmol),Pd(OAc)2(0.0682g,0.30mmol),PPh3(0.1579g,0.60mmol),CuI(0.5800g,3.0mmol),DBU(0.9047g,6.0mmol)和异丙基N-间甲基苯基咪唑啉环(0.6152g,3.0mmol),DMF(12mL),110℃条件下回流搅拌48小时,恢复到室温后,加入10%稀氨水溶液洗涤三次,加入无水硫酸钠干燥,减压旋蒸去除溶剂,通过柱层析(洗脱剂PE/EA=5/1)分离得到0.9130g Lm,为黄色油状产物(1.9mmol,64%yield).Optical Rotation:[α]20 D=-0.6(c 1.145,CHCl3).IR(neat):2957,2922,2871,2193,1600,1471;1H NMR:(400MHz,CHCl3)δ8.35(d,J=8.7Hz,1H),8.13(d,J=8.7Hz,1H),8.04(d,J=6.9Hz,1H),7.91(d,J=8.1Hz,1H),7.64(t,J=7.5Hz,1H),7.05(d,J=7.6Hz,2H),6.93(t,J=7.3Hz,1H),6.69(t,J=7.9Hz,1H),6.49(d,J=7.6Hz,1H),6.42(s,1H),6.33(d,J=8.2Hz,1H),4.20-4.05(m,2H),3.93-3.89(m,1H),2.07(s,4H),1.98(s,3H),1.95(d,J=3.6Hz,6H),1.13(d,J=6.8Hz,3H),1.06(d,J=6.8Hz,3H);13C NMR:(100MHz,CHCl3)δ163.6,160.3,153.7,145.4,144.4,141.4,137.8,136.5,133.0,130.7,129.4,128.5,128.1,127.3,121.8,121.7,119.2,118.3,77.3,77.0,76.7,53.5,35.8,34.7,32.8,31.6,31.5,18.9,18.0;HRMS(ESI)calculated for[C40H51N4]+(M+H+),requires m/z 587.4108,foundm/z 587.4111.
实施例2金属配合物B的制备
实施例B1:
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氮气保护下,Ll(0.2587g,0.50mmol,1.0equiv)和氯化亚铁(0.0610g,0.475mmol,0.95equiv)于2.0mL四氢呋喃中,常温反应4小时,旋干,加入少量乙醚洗涤,抽滤,干燥,得到0.2206g(0.34mmol,72%yield)的金属配合物B1。Anal.Calcd for C35H40Cl2FeN4+H2O:C,63.55;H,6.40;N,8.47;Found:C,63.95;H,6.48;N,8.30.
氮气保护下,Lb(0.2659g,0.50mmol,1.0equiv)和氯化亚铁(0.0603g,0.475mmol,0.95equiv)于2.0mL四氢呋喃中,常温反应4小时,旋干,加入少量乙醚洗涤,抽滤,干燥,得到0.1956g(0.30mmol,63%yield)的金属配合物B2。Anal.Calcd for C36H42Cl2FeN4+2H2O:C,62.35;H,6.69;N,8.08;Found:C,62.93;H,6.46;N,8.19.
氮气保护下,Lm(0.2535g,0.50mmol,1.0equiv)和氯化亚铁(0.0616g,0.475mmol,0.95equiv)于2.0mL四氢呋喃中,常温反应4小时,旋干,加入少量乙醚洗涤,抽滤,干燥,得到0.2171g(0.35mmol,73%yield)的金属配合物B3。Anal.Calcd for C34H38Cl2FeN4+2H2O:C,61.37;H,6.36;N,8.42;Found:C,61.93;H,6.11;N,8.53.
氮气保护下,Lk(0.2917g,0.50mmol,1.0equiv)和氯化亚铁(0.0601g,0.475mmol,0.95equiv)于2.0mL四氢呋喃中,常温反应4小时,旋干,加入少量乙醚洗涤,抽滤,干燥,得到0.2461g(0.37mmol,77%yield)的金属配合物B4。Anal.Calcd for C36H42Cl2FeN4O+H2O:C,62.53;H,6.41;N,8.10;Found:C,62.19;H,6.18;N,8.14.
实施例3金属配合物B1催化的烷基烯烃的不对称氢化反应
室温下,在一个干燥的反应试管中加入(手性)FeCl2-8-IIQ络合物B1(0.025mmol),烯烃(0.5mmol),n-C18H37SiH3(0.10mmol),置换三次氮气后,加入乙腈(0.10mmol),甲苯(1mL),三乙基硼氢化钠(0.075mmol),插入H2气球,然后在室温下搅拌12小时后,所得反应液通过硅胶短柱过滤,滤液蒸除溶剂得到产物。
实施例C1:1-(3,4-dimethyl-3l3-pentyl)-4-methoxybenzene
油状液体,66%产率,85%ee.Optical Rotation:[α]20 D=-1.8(c 1.165,CHCl3).HPLC conditions:Chiralcel OB-H,n-hexane/i-PrOH=99.5/0.5,1.0mL/min,n=220nm,tr 9.3(major),10.2(minor);1H NMR:(400MHz,CDCl3)δ7.10(d,J=8.5Hz,2H),6.83(d,J=8.5Hz,2H),3.79(s,3H),2.65-2.57(m,1H),2.50-2.42(m,1H),1.66-1.58(m,2H),1.43-1.30(m,2H),0.86(d,J=6.7Hz,6H),0.81(d,J=6.9Hz,3H);产物数据与已知物一致[P.Lu,X.Ren,H.Xu,D.Lu,Y.Sun,Z.LuJ.Am.Chem.Soc.2021,143,12433–12438]
实施例C2:
油状液体,50%产率,25%ee.HPLC conditions:Chiralcel OB-H,n-hexane/i-PrOH=99.5/0.5,1.0mL/min,n=220nm,tr 9.3(major),10.2(minor);1H NMR:(400.1MHz,)δ7.10(d,J=8.6Hz,2H),6.82(d,J=8.6Hz,2H),3.79(s,3H),2.66-2.46(m,2H),1.43-1.34(m,2H),1.23-1.14(m,2H),0.92-0.85(m,6H);产物数据与已知物一致[S.Bell,B,Wüstenberg,S.Kaiser,F,Menges,T.Netscher,A.Pfaltz Science 2006,311,642–644.]
a反应条件为烯烃(0.5mmol),氢气球,硅烷(20mol%),乙腈(20mol%),催化剂(5mol%),还原剂三乙基硼氢化钠(15mol%),甲苯1mL,在室温(rt)或0℃反应12小时。b产物鉴定和产率由核磁氢谱采用内标法(三甲基苯硅烷)检测。c ee值由液相色谱(手性OB-H柱)检测。
以上列举的仅是本发明的一些具体实施例,显然,本发明不限于以上实施例,还可以有许多变形,本领域的普通技术人员能从本发明公开的内容直接导出或联想到的所有变形,均应认为是本发明的保护范围。
Claims (7)
1.一种手性含亚胺喹啉咪唑啉类化合物,所述的化合物是高光学纯的,所述高光学纯是指有90%以上的对映体选择性,结构式如下式(1)所示:
式(1)中,*代表手性碳原子;
R1是2,6-二甲基苯基、2,6-二乙基苯基、2,6-二异丙基苯基或2,6-二异丙基-4-甲氧基苯基;
R2是甲基、乙基、异丙基或叔丁基;
R3、R4、R5、R6、R7各自独立为H、甲基、乙基、异丙基或叔丁基;
R8、R9各自独立为H、甲基、乙基、异丙基或叔丁基;
R10为乙基、异丙基、叔丁基、仲丁基、苯基或苄基,
R11是苄基或苯基。
2.如权利要求1所述的手性含亚胺喹啉咪唑啉类化合物,其特征在于所述R3、R4、R5、R6、R7均为H;R8、R9均为H;
R10为乙基、异丙基、叔丁基、仲丁基或苄基。
3.如权利要求1所述的手性含亚胺喹啉咪唑啉类化合物的制备方法,其特征在于所述的方法为:
氮气保护下,式(4)所示的化合物与式(5)所示的咪唑啉类化合物在过渡金属无机盐和有机膦配体、有机碱、一价铜盐催化下进行偶联反应,制得式(1)所示的手性含亚胺喹啉咪唑啉类化合物;所述过渡金属无机盐是指Ru、Rh、Pd、Ir的无机盐;所述有机碱为1,8-二氮杂双环[5.4.0]十一碳-7-烯;所述有机膦配体为三苯基膦,一价铜盐为碘化亚铜;
R1~R11的定义如权利要求1所述。
4.一种手性含亚胺喹啉咪唑啉类化合物的金属络合物,其特征在于所述金属络合物是由权利要求1所述的手性含亚胺喹啉咪唑啉类化合物与过渡金属盐MEn络合反应制得,手性含亚胺喹啉咪唑啉类化合物的金属络合物的通式如下式(6)所示:
式(6)中,R1-R11、*如权利要求1所述;
式(6)中,M为过渡金属Fe、Co、Ni、Cu、Ag、Au、Ru、Rh、Pd、Os或Ir;
Ε为F、Cl、Br、I、氰化物、氰酸根、四氟硼酸根、异氰酸根、碳酸根、甲酸根、乙酸根、丙酸根、甲基磺酸根、三氯甲基磺酸根、苯基磺酸根、甲苯磺酸根、磷酸根中的任意一种;
n为E的个数,为1、2或3。
5.如权利要求4所述的手性含亚胺喹啉咪唑啉类化合物的金属络合物,其特征在于所述手性含亚胺喹啉咪唑啉类化合物的金属络合物为以下之一:
。
6.如权利要求4或5所述的手性含亚胺喹啉咪唑啉类化合物的金属络合物的制备方法,其特征在于所述方法为:
氮气保护下,式(1)所示的手性含亚胺喹啉咪唑啉类化合物和过渡金属盐MEn在有机溶剂中反应1~10小时,制得式(6)所示的手性含亚胺喹啉咪唑啉类化合物的金属络合物。
7.如权利要求4或5所述的手性含亚胺喹啉咪唑啉类化合物的金属络合物作为催化剂,在催化1,1-二烷基烯烃类化合物的不对称氢化反应制备手性或非手性的烷烃化合物中的应用;应式如式(i)所示;
Ra=Rb产物没有手性
Ra≠Rb产物具有手性
式(A)为1,1-二烷基烯烃化合物,Ra、Rb各自独立为C1~C10的烷基,所述烷基上的H不被取代或者被一个以上的取代基C取代,所述的取代基C为C1-C4烷氧基、苯基或萘基;
所述苯基或萘基上的H不被取代或被一个以上的取代基D取代,所述的取代基D为C1-C4烷基、C1-C4烷氧基、C1-C4硅烷基或卤素。
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