WO2009125565A1 - ルテニウム化合物及び光学活性アミノアルコール化合物の製造方法 - Google Patents
ルテニウム化合物及び光学活性アミノアルコール化合物の製造方法 Download PDFInfo
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- WO2009125565A1 WO2009125565A1 PCT/JP2009/001569 JP2009001569W WO2009125565A1 WO 2009125565 A1 WO2009125565 A1 WO 2009125565A1 JP 2009001569 W JP2009001569 W JP 2009001569W WO 2009125565 A1 WO2009125565 A1 WO 2009125565A1
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- -1 aminoalcohol compound Chemical class 0.000 title claims abstract description 97
- 150000003304 ruthenium compounds Chemical class 0.000 title claims abstract description 49
- 238000004519 manufacturing process Methods 0.000 title claims description 18
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 84
- 239000003446 ligand Substances 0.000 claims description 60
- 125000003118 aryl group Chemical group 0.000 claims description 47
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 46
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 42
- 125000001424 substituent group Chemical group 0.000 claims description 41
- 125000005843 halogen group Chemical group 0.000 claims description 33
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 33
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 15
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 15
- 150000004985 diamines Chemical class 0.000 claims description 14
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims description 10
- 125000003358 C2-C20 alkenyl group Chemical group 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 9
- 125000000962 organic group Chemical group 0.000 claims description 8
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 8
- 125000006554 (C4-C8) cycloalkenyl group Chemical group 0.000 claims description 5
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- 125000000753 cycloalkyl group Chemical group 0.000 claims description 5
- SSJXIUAHEKJCMH-UHFFFAOYSA-N cyclohexane-1,2-diamine Chemical compound NC1CCCCC1N SSJXIUAHEKJCMH-UHFFFAOYSA-N 0.000 claims description 5
- 125000003161 (C1-C6) alkylene group Chemical group 0.000 claims description 4
- WDYGPMAMBXJESZ-UHFFFAOYSA-N 1,1-bis(4-methoxyphenyl)-3-methylbutane-1,2-diamine Chemical compound C1=CC(OC)=CC=C1C(N)(C(N)C(C)C)C1=CC=C(OC)C=C1 WDYGPMAMBXJESZ-UHFFFAOYSA-N 0.000 claims description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- 125000000061 phosphanyl group Chemical group [H]P([H])* 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 abstract description 15
- 150000001728 carbonyl compounds Chemical class 0.000 abstract description 9
- 150000001875 compounds Chemical class 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 17
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 16
- 239000001257 hydrogen Substances 0.000 description 15
- 229910052739 hydrogen Inorganic materials 0.000 description 15
- 238000006722 reduction reaction Methods 0.000 description 14
- 239000000047 product Substances 0.000 description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- 229910052707 ruthenium Inorganic materials 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- 230000035484 reaction time Effects 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 6
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 6
- DHCWLIOIJZJFJE-UHFFFAOYSA-L dichlororuthenium Chemical compound Cl[Ru]Cl DHCWLIOIJZJFJE-UHFFFAOYSA-L 0.000 description 6
- FVZVCSNXTFCBQU-UHFFFAOYSA-N phosphanyl Chemical group [PH2] FVZVCSNXTFCBQU-UHFFFAOYSA-N 0.000 description 6
- 125000003367 polycyclic group Chemical group 0.000 description 6
- 125000006552 (C3-C8) cycloalkyl group Chemical group 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 125000000623 heterocyclic group Chemical group 0.000 description 5
- 238000004128 high performance liquid chromatography Methods 0.000 description 5
- 150000002430 hydrocarbons Chemical group 0.000 description 5
- WDYGPMAMBXJESZ-SFHVURJKSA-N (2s)-1,1-bis(4-methoxyphenyl)-3-methylbutane-1,2-diamine Chemical compound C1=CC(OC)=CC=C1C(N)([C@@H](N)C(C)C)C1=CC=C(OC)C=C1 WDYGPMAMBXJESZ-SFHVURJKSA-N 0.000 description 4
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- 239000012327 Ruthenium complex Substances 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- GPFIUEZTNRNFGD-UHFFFAOYSA-N bis(3,5-dimethylphenyl)phosphane Chemical compound CC1=CC(C)=CC(PC=2C=C(C)C=C(C)C=2)=C1 GPFIUEZTNRNFGD-UHFFFAOYSA-N 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 229960001701 chloroform Drugs 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- 238000002955 isolation Methods 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- 0 *c1ccc(cccc2)c2c1-c1c(cccc2)c2ccc1* Chemical compound *c1ccc(cccc2)c2c1-c1c(cccc2)c2ccc1* 0.000 description 3
- PONXTPCRRASWKW-UHFFFAOYSA-N 1,2-diphenylethane-1,2-diamine Chemical compound C=1C=CC=CC=1C(N)C(N)C1=CC=CC=C1 PONXTPCRRASWKW-UHFFFAOYSA-N 0.000 description 3
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- 125000000041 C6-C10 aryl group Chemical group 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 125000003828 azulenyl group Chemical group 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000003392 indanyl group Chemical group C1(CCC2=CC=CC=C12)* 0.000 description 3
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 125000002950 monocyclic group Chemical group 0.000 description 3
- RLEBYZJBMZZXSZ-XJKSGUPXSA-N n-[(1s,2s)-1-hydroxy-1-phenylpropan-2-yl]-n-methylbenzamide Chemical compound C1([C@H](O)[C@H](C)N(C)C(=O)C=2C=CC=CC=2)=CC=CC=C1 RLEBYZJBMZZXSZ-XJKSGUPXSA-N 0.000 description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000001624 naphthyl group Chemical group 0.000 description 3
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 125000005329 tetralinyl group Chemical group C1(CCCC2=CC=CC=C12)* 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- RRKODOZNUZCUBN-CCAGOZQPSA-N (1z,3z)-cycloocta-1,3-diene Chemical compound C1CC\C=C/C=C\C1 RRKODOZNUZCUBN-CCAGOZQPSA-N 0.000 description 2
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- SMWUDAKKCDQTPV-UHFFFAOYSA-N 1,3-dimethylimidazolidine Chemical compound CN1CCN(C)C1 SMWUDAKKCDQTPV-UHFFFAOYSA-N 0.000 description 2
- JELCTTFEQUFDER-UHFFFAOYSA-N 1-(4-methoxyphenyl)-3-methylbutane-1,2-diamine Chemical compound COC1=CC=C(C(N)C(N)C(C)C)C=C1 JELCTTFEQUFDER-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 2
- 125000006024 2-pentenyl group Chemical group 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 125000003860 C1-C20 alkoxy group Chemical group 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- FNHLWKCEIWYLOM-UHFFFAOYSA-N [2-[2-bis(3,5-dimethylphenyl)phosphanyl-6-methylphenyl]-3-methylphenyl]-bis(3,5-dimethylphenyl)phosphane Chemical group CC1=CC(C)=CC(P(C=2C=C(C)C=C(C)C=2)C=2C(=C(C)C=CC=2)C=2C(=CC=CC=2C)P(C=2C=C(C)C=C(C)C=2)C=2C=C(C)C=C(C)C=2)=C1 FNHLWKCEIWYLOM-UHFFFAOYSA-N 0.000 description 2
- DILUSYFTBYRNPG-UHFFFAOYSA-L [Ru](Cl)Cl.C1(=CC(=CC(=C1)C)C)PC1=CC(=CC(=C1)C)C Chemical compound [Ru](Cl)Cl.C1(=CC(=CC(=C1)C)C)PC1=CC(=CC(=C1)C)C DILUSYFTBYRNPG-UHFFFAOYSA-L 0.000 description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 235000019445 benzyl alcohol Nutrition 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 125000000392 cycloalkenyl group Chemical group 0.000 description 2
- 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 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- PONXTPCRRASWKW-KBPBESRZSA-N diphenylethylenediamine Chemical compound C1([C@H](N)[C@@H](N)C=2C=CC=CC=2)=CC=CC=C1 PONXTPCRRASWKW-KBPBESRZSA-N 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 239000000852 hydrogen donor Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- HFPZCAJZSCWRBC-UHFFFAOYSA-N p-cymene Chemical compound CC(C)C1=CC=C(C)C=C1 HFPZCAJZSCWRBC-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- CUQOHAYJWVTKDE-UHFFFAOYSA-N potassium;butan-1-olate Chemical compound [K+].CCCC[O-] CUQOHAYJWVTKDE-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 125000004916 (C1-C6) alkylcarbonyl group Chemical group 0.000 description 1
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 description 1
- 125000006719 (C6-C10) aryl (C1-C6) alkyl group Chemical group 0.000 description 1
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
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- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000004344 phenylpropyl group Chemical group 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000000711 polarimetry Methods 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical class [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Chemical group 0.000 description 1
- 239000011593 sulfur Chemical group 0.000 description 1
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C07—ORGANIC CHEMISTRY
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/5022—Aromatic phosphines (P-C aromatic linkage)
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
- B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B53/00—Asymmetric syntheses
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/16—Preparation of optical isomers
- C07C231/18—Preparation of optical isomers by stereospecific synthesis
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- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0046—Ruthenium compounds
- C07F15/0053—Ruthenium compounds without a metal-carbon linkage
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- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F17/00—Metallocenes
- C07F17/02—Metallocenes of metals of Groups 8, 9 or 10 of the Periodic System
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/655—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms
- C07F9/65515—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms the oxygen atom being part of a five-membered ring
- C07F9/65517—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms the oxygen atom being part of a five-membered ring condensed with carbocyclic rings or carbocyclic ring systems
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
- B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
- B01J2231/643—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of R2C=O or R2C=NR (R= C, H)
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0202—Polynuclearity
- B01J2531/0205—Bi- or polynuclear complexes, i.e. comprising two or more metal coordination centres, without metal-metal bonds, e.g. Cp(Lx)Zr-imidazole-Zr(Lx)Cp
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
- B01J2531/0244—Pincer-type complexes, i.e. consisting of a tridentate skeleton bound to a metal, e.g. by one to three metal-carbon sigma-bonds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/821—Ruthenium
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- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/07—Optical isomers
Definitions
- the present invention relates to a method for producing an optically active amino alcohol compound that asymmetrically reduces a carbonyl compound, particularly an ⁇ -aminoketone compound, using the novel ruthenium compound useful as an asymmetric reduction catalyst for the carbonyl compound, and to the novel ruthenium compound.
- a method for catalytically asymmetric reduction of carbonyl compounds such as ketones is known as a method for producing optically active alcohol compounds.
- a method using a rhodium complex described in Non-Patent Documents 1 and 2 a method using an iridium complex described in Non-Patent Document 3, a method by hydrogen transfer using ruthenium as a catalyst described in Patent Document 1, a patent A hydrogenation method using ruthenium described in Document 2 as a catalyst is known.
- Non-Patent Documents 1 to 3 are so-called noble metals such as rhodium and iridium in which the metal used as the catalyst is relatively expensive, and have a low hydrogenation activity and are asymmetric reduction catalysts. In the case of using as, it requires a relatively high temperature or high hydrogen pressure.
- the method described in Patent Document 1 must use an organic compound such as formic acid as a hydrogen source, which is disadvantageous in terms of operation and cost as compared to using an inexpensive hydrogen source such as hydrogen gas.
- Patent Document 2 is an excellent method for asymmetric reduction of carbonyl compounds, but an expensive bidentate phosphine ligand having a plurality of substituents and a diamine ligand that is difficult to synthesize. There was a problem that good results could not be obtained unless a catalyst having the above was used. Therefore, development of an inexpensive asymmetric hydrogenation catalyst capable of producing a corresponding optically active alcohol compound from a carbonyl compound with high selectivity and high yield using an inexpensive hydrogen source such as hydrogen gas has been desired.
- ruthenium catalysts have been developed so far, and among them, some typical ones will be described particularly regarding ruthenium catalysts having a phosphine ligand similar to the present invention.
- Formula (1) (In the formula, X and Y may be the same or different and each represents a hydrogen atom, a halogen atom, a carboxyl group or another anion group, and R 1 , R 2 and R 3 may be the same. It is a hydrocarbon group which may be different and may have a substituent, and R 1 and R 2 together may form a carbon chain ring which may have a substituent. , N is an integer of 0 to 4, R 6 , R 7 and R 8 may be the same or different and each represents a hydrogen atom or a hydrocarbon group which may have a substituent, and m is 0 To an integer from 4 to 4)) (Patent Document 2).
- X and Y each independently represent a hydrogen atom, a halogen atom, a carboxyl group, a hydroxyl group or a C1-20 alkoxy group
- Px represents a phosphine ligand
- R 1 to R 8 each represent Independently, a hydrogen atom, an optionally substituted C1-20 alkyl group, an optionally substituted C2-20 alkenyl group, an optionally substituted C3-8 cycloalkyl group
- the aralkyl group which may have a substituent, or the aryl group which may have a substituent is represented.
- any of R 1 and R 2 may be bonded to any of R 3 and R 4 , and any of R 5 and R 6 may be bonded to any of R 7 and R 8 to form a ring.
- A may have a substituent and may have an ether bond, C1-3 alkylene, may have a substituent, C3-8 cycloalkylene, and may have a substituent.
- An arylene or a divalent heterocyclic ring optionally having a substituent is represented.
- A is alkylene
- any of R 1 and R 2 may be bonded to any of R 5 and R 6 to form a ring.
- Formula (3) [Wherein, X and Y each independently represent a hydrogen atom, a halogen atom, a carboxyl group, a hydroxyl group, or a C1-20 alkoxy group.
- Px represents a phosphine ligand, and n represents 1 or 2.
- A represents a diamine ligand represented by the following formula (4) or formula (5).
- R 1 is an optionally substituted C1-20 alkyl group, an optionally substituted C2-20 alkenyl group, an optionally substituted C3-8 cycloalkyl group, A C7-20 aralkyl group which may have a substituent, an aryl group which may have a substituent, or a heterocyclic group which may have a substituent;
- R 2 and R 3 each independently It has a hydrogen atom, an optionally substituted C1-20 alkyl group, an optionally substituted C2-20 alkenyl group, an optionally substituted C3-8 cycloalkyl group or a substituent.
- R 2 and R 3 may be bonded together to form a ring, provided that R 2 and R 3 are both hydrogen atoms.
- An object of the present invention is to use a novel ruthenium compound useful as an asymmetric reduction catalyst for a carbonyl compound, in particular, to perform asymmetric reduction of an ⁇ -aminoketone and to produce a corresponding optically active aminoalcohol highly stereoselectively, and It is to provide a method for producing in a high yield, and this new ruthenium compound that is easily available.
- the present invention (1) Formula (I) [Wherein, X represents a halogen atom.
- Pxx is the formula (II) [Wherein R 5 represents the formula (III) (Wherein R a is a hydrogen atom, a halogen atom, a C1-6 alkyl group, a C1-6 alkoxy group or a C6-18 aryl group, and R b is a halogen atom, a C1-6 alkyl group, a C1-6 alkoxy group) Represents a phenyl group having a substituent represented by the following formula: or a C6-18 aryl group.
- A represents a divalent organic group.
- R 1 R 2 C (NH 2 ) —R 3 R 4 C (NH 2 ) represents an optically active diamine ligand.
- R 1 to R 4 each independently represents a hydrogen atom, an unsubstituted or substituted C1-20 alkyl group, an unsubstituted or substituted C2-20 alkenyl group, an unsubstituted or substituted C3-8 A cycloalkyl group, an unsubstituted or substituted C4-8 cycloalkenyl group, an unsubstituted or substituted C6-18 aryl group, or an unsubstituted or substituted C7-18 aralkyl group, R 1 and R Any of 2 may be bonded to any of R 3 and R 4 to form a ring.
- a ruthenium compound represented by formula (IV) in the presence of the ruthenium compound, particularly an ⁇ -aminoketone compound (Wherein R 10 and R 11 are each independently a C1-6 alkyl group having an unsubstituted or substituted group or a C6-18 aryl group having an unsubstituted or substituted group, and R 12 and R 13 are A hydrogen atom, an unsubstituted or substituted C1-6 alkyl group, an unsubstituted or substituted C6-18 aryl group, an R 14 CO— group or an R 14 OCO— group, wherein R 14 is unsubstituted or Represents a C1-6 alkyl group having a substituent or a C6-18 aryl group having no substituent or a substituent, and R 10 and R 11 and R 12 and R 13 may be bonded to each other to form a ring; And ⁇ ) -aminoketone compound represented by (2) is hydrogenated.
- the method for producing the optically active amino alcohol compound of the present invention preferably comprises: (3) The method for producing an optically active amino alcohol compound according to (2), wherein in the formula (IV), R 10 is an unsubstituted or substituted phenyl group, (4)
- the optically active bidentate phosphine ligand represented by the formula (II) is represented by the formula (II-B): (Wherein R 5 represents the same meaning as described above), an optically active bidentate phosphine ligand represented by the formula (II-C) (Wherein R 5 represents the same meaning as described above), an optically active bidentate phosphine ligand represented by the formula (II-D) (Wherein R 5 represents the same meaning as described above), an optically active bidentate phosphine ligand represented by the formula (II-E) (Wherein R 5 represents the same meaning as described above.
- R d represents a C1-6 alkyl group, a C1-6 alkoxy group, a halogen atom or a trifluoromethyl group.
- R e represents a hydrogen atom
- C1— 6 represents an alkyl group, a C1-6 alkoxy group, or a halogen atom
- R f represents a hydrogen atom, a C1-6 alkyl group, or a C1-6 alkoxy group).
- Formula (II-F) (Wherein R 5 represents the same meaning as described above.
- R g represents a hydrogen atom or an unsubstituted or substituted C1-6 alkyl group.
- R h represents a hydrogen atom or an unsubstituted or substituted group.
- R i and R j each independently represents an unsubstituted or substituted C1-6 alkyl group or an unsubstituted or substituted C6-18. Represents an aryl group, R i and R j may combine to form a ring, and B represents a single bond or an unsubstituted or substituted C1-6 alkylene group.
- optically active amino alcohol compound according to (2) or (3) which is any one of active bidentate phosphine ligands, (5)
- the optically active bidentate phosphine ligand represented by the formula (II) is represented by the formula (II-A): (Wherein R c represents a C1-6 alkyl group, a C1-6 alkoxy group, a halogen atom or a trifluoromethyl group.
- R 5 represents the same meaning as described above.
- the optically active bidentate phosphine ligand represented by the above formula (II-A) is 2,2′-bis [bis (3,5-dimethylphenyl) phosphanyl] -6,6′-dimethyl-
- the optically active diamine ligand is 1,1-bis (4-methoxyphenyl) -2-isopropyl-1,2-ethanediamine, 1,2
- the ruthenium compound of the present invention is preferably (8) Formula (IA) [Wherein, X represents a halogen atom.
- P a xx has the formula (II-A) [Wherein R c represents a C1-6 alkyl group, a C1-6 alkoxy group, a halogen atom or a trifluoromethyl group.
- R 5 represents the formula (III) (Wherein R a is a hydrogen atom, a halogen atom, a C1-6 alkyl group, a C1-6 alkoxy group or a C6-18 aryl group, and R b is a halogen atom, a C1-6 alkyl group, a C1-6 alkoxy group) Represents a phenyl group having a substituent represented by the following formula: or a C6-18 aryl group. ]
- R 1 R 2 C (NH 2 ) —R 3 R 4 C (NH 2 ) represents an optically active diamine ligand.
- R 1 to R 4 each independently represents a hydrogen atom, an unsubstituted or substituted C1-20 alkyl group, an unsubstituted or substituted C2-20 alkenyl group, an unsubstituted or substituted C3-8 A cycloalkyl group, an unsubstituted or substituted C4-8 cycloalkenyl group, an unsubstituted or substituted C6-18 aryl group, or an unsubstituted or substituted C7-18 aralkyl group, R 1 and R Any of 2 may be bonded to any of R 3 and R 4 to form a ring.
- the optically active bidentate phosphine ligand represented by the formula (II-A) is 2,2′-bis [bis (3,5 -Dimethylphenyl) phosphanyl] -6,6′-dimethyl-1,1′-biphenyl, which is a ruthenium compound according to (8), (10)
- the optically active diamine ligand is 1,1-bis (4-methoxyphenyl) -2-isopropyl-1,2-ethanediamine, The ruthenium compound according to (8) or (9), which is 1,2-diphenyl-1,2-ethanediamine or 1,2-diaminocyclohexane.
- the ruthenium compound of the present invention can produce an optically active amino alcohol compound from ⁇ -amino ketones with high stereoselectivity and high yield.
- R 5 represents formula (III) The phenyl group which has a substituent represented by these is represented.
- R a represents a hydrogen atom, a halogen atom, a C1-6 alkyl group, a C1-6 alkoxy group or a C6-18 aryl group
- Rb represents a halogen atom, a C1-6 alkyl group, a C1-6 alkoxy group. Or a C6-18 aryl group.
- A represents a divalent organic group.
- the divalent organic group represents all divalent functional groups containing 2 to 60 carbon atoms, and optionally any 1 to 30 heteroatoms independently selected from oxygen, nitrogen and sulfur. May be included.
- the divalent organic group includes: a C1-8 alkyl group; a divalent organic group composed of a C6-18 aryl group such as a biphenyl group or a binaphthalenyl group; a divalent composed of a heterocycle such as a pyrrolidine or a bipyridinyl group.
- ferrocene in which two upper and lower cyclopentadienyl anions are coordinated to iron (II) ions can also be used as the divalent organic group. These may further have a substituent.
- “C1-8 alkylene group” includes methylene, ethylene, trimethylene and the like.
- Halogen atom represents fluorine, chlorine, bromine, iodine or the like.
- C1-6 alkyl group includes methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, t-pentyl, hexyl and the like.
- C1-6 alkoxy includes methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, t-butoxy and the like.
- the “C6-18 aryl group” is a monocyclic or polycyclic C6-18 aryl group. In the case of a polycyclic aryl group, a partially saturated group is also included in addition to a fully unsaturated group. Examples include phenyl, naphthyl, azulenyl, indenyl, indanyl, tetralinyl and the like. Preferably, it is a C6-10 aryl group.
- optically active bidentate phosphine ligand examples include those represented by the general formula (II-B) (Wherein R 5 represents formula (III) (Wherein R a is a hydrogen atom, a halogen atom, a C1-6 alkyl group, a C1-6 alkoxy group or a C6-18 aryl group, and R b is a halogen atom, a C1-6 alkyl group, a C1-6 alkoxy group) Represents a phenyl group having a substituent represented by the following formula: or a C6-18 aryl group.
- the phosphine ligand represented by this can be mentioned.
- R 5 is preferably a 3,5-dimethylphenyl group.
- R 5 is preferably a 3,5-dimethylphenyl group.
- R 5 is preferably a 3,5-dimethylphenyl group.
- the general formula (II-E) (.R d wherein, R 5 is of the same meanings as defined above, C1 ⁇ 6 alkyl group, C1 ⁇ 6 alkoxy group, a halogen atom, is .
- R e represents a trifluoromethyl group, a hydrogen atom, C1 ⁇ 6 alkyl group, C1-6 alkoxy group, halogen atom, Rf represents hydrogen atom, C1-6 alkyl group, C1-6 alkoxy group).
- C1-6 alkyl group” and “C1-6 alkoxy group” of R d , R e and R f can be the same substituents as those exemplified in formula (III). Specifically, (4,4 ′, 6,6′-tetramethyl-5,5′-dimethoxybiphenyl-2,2′-diyl) -bis (bis (3,5-dimethylphenyl) phosphine), ( 4,4 ′, 6,6′-tetratrifluoromethylbiphenyl-2,2′-diyl) -bis (bis (3,5-dimethylphenyl) phosphine), (4,6-ditrifluoromethyl-4 ′, 6'-dimethyl-5'-methoxybiphenyl-2,2'-diyl) -bis (bis (3,5-dimethylphenyl) phosphine), (4,4 ', 5,5', 6,6'-tetra Hexam
- R 5 represents the same meaning as described above; R c represents a C1-6 alkyl group, a C1-6 alkoxy group, a halogen atom, or a trifluoromethyl group).
- R c represents a C1-6 alkyl group, a C1-6 alkoxy group, a halogen atom, or a trifluoromethyl group.
- R 5 is preferably a 3,5-dimethylphenyl group.
- R 5 represents the same meaning as described above.
- R g represents a hydrogen atom or an unsubstituted or substituted C1-6 alkyl group.
- R h represents a hydrogen atom or an unsubstituted or substituted group.
- Specific examples of the “C1-6 alkyl group” for R g and R h include the same substituents as those exemplified in Formula (III).
- R 5 is preferably a 3,5-dimethylphenyl group. Specific examples include 1 ′, 2-bis [bis (3,5-dimethylphenyl) phosphino] ferrocenylethane.
- R i and R j each independently represents an unsubstituted or substituted C1-6 alkyl group or an unsubstituted or substituted C6-18. Represents an aryl group, R i and R j may combine to form a ring, and B represents a single bond or an unsubstituted or substituted C1-6 alkylene group. Mention may be made of active bidentate phosphine ligands.
- C1-6 alkyl group and “C6-18 aryl group” for R i and R j include the same substituents as those exemplified in Formula (III).
- C1-6 alkylene group includes methylene, ethylene, trimethylene and the like.
- R 5 is preferably a 3,5-dimethylphenyl group.
- 2,3-bis (bis (3,5-dimethylphenyl) phosphino) butane 1,2-bis (bis (3,5-dimethylphenyl) phosphino) propane, 5,6-bis (bis (3,5-dimethylphenyl) phosphino) -2-norbornene, 1-benzoyl-3,4-bis (bis (3,5-dimethylphenyl) phosphino) pyrrolidine, 2,4-bis (bis (3,5- And dimethylphenyl) phosphino) pentane and 2,3-o-isobropyridene-2,3-dihydroxy-1,4-bis (bis (3,5-dimethylphenyl) phosphino) butane.
- optically active bidentate phosphine ligand examples include (4,4 ′, 6,6′-tetramethyl-2,2′-biphenylene) -bis (bis (3,5-dimethyl). Phenyl) phosphine), (3,3 ′, 6,6′-tetramethyl-2,2′-biphenylene) -bis (bis (3,5-dimethylphenyl) phosphine), (4,4′-difluoro-6 , 6'-dimethyl-2,2'-biphenylene) -bis (bis (3,5-dimethylphenyl) phosphine), (4,4'-bis (dimethylamino) -6,6'-dimethyl-2,2 '-Biphenylene) -bis (bis (3,5-dimethylphenyl) phosphine), 1,11-bis (bis (3,5-dimethylphenyl) phosphino) -5,
- R 1 R 2 C (NH 2 ) —R 3 R 4 C (NH 2 ) represents an optically active diamine ligand.
- R 1 to R 4 each independently represents a hydrogen atom, an unsubstituted or substituted C1-20 alkyl group, an unsubstituted or substituted C2-20 alkenyl group, an unsubstituted or substituted C3-8 A cycloalkyl group, an unsubstituted or substituted C4-8 cycloalkenyl group, an unsubstituted or substituted C6-18 aryl group, or an unsubstituted or substituted C7-18 aralkyl group, R 1 and R Any of 2 may be bonded to any of R 3 and R 4 to form a ring.
- C1-20 alkyl group of “unsubstituted or substituted C1-20 alkyl group” means methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, t-butyl, n-pentyl, Including isopentyl, neopentyl, t-pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl and the like. Preferably, it is a C1-6 alkyl group.
- C2-20 alkenyl group of “unsubstituted or substituted C2-20 alkenyl group” means ethenyl, n-propenyl, isopropenyl, n-butenyl, sec-butenyl, t-butenyl, 1,3-butadienyl N-pentenyl, 2-pentenyl, 3-pentenyl, 2-hexenyl, 2-decenyl, 2-dodecenyl and the like.
- it is a C2-6 alkenyl group.
- C3-8 cycloalkyl group in “unsubstituted or substituted C3-8 cycloalkyl group” means an alkyl group having a cyclic moiety, and is cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclopentyl. Including ethyl, cyclohexylmethyl and the like.
- C4-6 cycloalkenyl group in the “unsubstituted or substituted C4-6 cycloalkenyl group” means an alkenyl group having a cyclic moiety and includes 2-cyclobutenyl, 2-cyclohexenyl, 2-cyclopentenylmethyl. Etc.
- the “C6-18 aryl group” in the “unsubstituted or substituted C6-18 aryl group” is a monocyclic or polycyclic C6-18 aryl group, and in the case of a polycyclic aryl group, it is completely unsaturated. In addition, partially saturated groups are also included. Examples include phenyl, naphthyl, azulenyl, indenyl, indanyl, tetralinyl and the like. Preferably, it is a C6-10 aryl group.
- the “C7-18 aralkyl group” of the “unsubstituted or substituted C7-18 aralkyl group” is a group in which an aryl group and an alkyl group are bonded, and includes benzyl, phenethyl, phenylpropyl, phenylbutyl, phenylhexyl, Includes naphthylmethyl and the like. Preferred is C6-10 aryl C1-6 alkyl.
- substituted or substituted is not particularly limited as long as it is chemically acceptable, but halogen atoms such as fluorine atom, chlorine atom, bromine atom, iodine atom; methyl group C1-6 alkyl groups such as ethyl group, n-propyl group, i-propyl group; vinyl group, 1-propenyl group, 2-propenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1 -C2-6 alkenyl groups such as methyl-2-propenyl group, 2-methyl-2-propenyl group, 1-pentenyl group, 2-pentenyl group, 4-hexenyl group and 5-hexenyl group; ethynyl group, 1-propynyl Group, 2-propynyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group, 1-methyl-2-propyl group, but halogen atoms such as fluor
- the ring in “any one of R 1 and R 2 may combine with any of R 3 and R 4 to form a ring” is not particularly limited as long as it is chemically acceptable, but preferably C5-8 hydrocarbon ring, and includes, for example, cyclopentane-1,2-diyl, cyclohexane-1,2-diyl, 4-cyclohexene-1,2-diyl and the like.
- the diamine ligand it is preferable that at least one of carbon atoms C of R 1 R 2 C (NH 2 ) —R 3 R 4 C (NH 2 ) is optically active.
- Specific examples of the diamine ligand include, but are not limited to, compounds comprising combinations of substituents shown in the following table. In the table, abbreviations have the following meanings. Ph: phenyl, c-Pr: cyclopropyl, c-He: cyclohexyl
- 1,1-bis (4-methoxyphenyl) -2- wherein at least one of R 1 to R 4 in formula (I) is a phenyl group that is unsubstituted or has a substituent.
- Isopropyl-1,2-ethanediamine, 1,2-diphenyl-1,2-ethanediamine, etc., or any of R 1 and R 2 is bonded to either R 3 or R 4 to form an alkyl ring 1,2-diaminocyclopentane, 1,2-diaminocyclohexane and the like.
- the ruthenium compound of formula (I) is preferably of formula (IA) It is represented by P a xx represents an optically active bidentate phosphine ligand represented by the above formula (II-A).
- X and R 1 R 2 C (NH 2 ) —R 3 R 4 C (NH 2 ) have the same meaning as described above.
- ruthenium compound of the present invention examples include ⁇ (S) -6,6'-bis [bis- (3,5-dimethyl-phenyl) -phosphanyl] -2,2'-dimethyl-biphenyl ⁇ ruthenium (II) dichloride (2S) -1,1-bis (4-Methoxyphenyl) -2-isopropyl 1,2-ethanediamine, ⁇ (S) -6,6′-bis [bis- (3,5-dimethyl-phenyl) -phosphanyl] -2,2′-dimethyl -Biphenyl ⁇ ruthenium (II) dichloride (1S, 2S) -1,2-diphenyl) -1,2-ethanediamine, ⁇ (S) -6,6'-bis [bis- (3,5-dimethyl-phenyl) ) -Phosphanyl] -2,2′-dimethyl-biphenyl ⁇ ruthenium (II)
- the ruthenium compound of the present invention can be produced by a known method (see Patent Document 2, Patent Document 3, and the like). For example, it can be produced by the following method.
- a starting material used in the method for producing a ruthenium compound 0 valent, 1 valent, 2 valent, 3 valent, and even higher valence ruthenium can be used.
- Angew. Chem. Int. Ed. 37, 1703 (1998) a method using a divalent ruthenium complex is simple. That is, a ruthenium compound represented by the formula (I) can be produced by adding a diamine compound after heating a solvent solution of a divalent ruthenium-halide complex and a bidentate phosphine ligand.
- a method for producing a ruthenium compound when a divalent ruthenium-halide complex is used as a starting material is as follows. First, a starting divalent ruthenium-halide complex and a bidentate phosphine ligand are reacted in a solvent by heating to obtain a corresponding phosphine-ruthenium-halide complex.
- the starting divalent ruthenium-halide complex is not particularly limited as long as it is a ruthenium complex having a ligand that can be substituted with a bidentate phosphine ligand and a diamine ligand.
- halogens coordinated with diene such as [ruthenium dichloride (norbornadiene)] polynuclear, [ruthenium dichloride (cyclooctadiene)] polynuclear, [bis (methylallyl) ruthenium (cyclooctadiene)].
- the amount of the bidentate phosphine ligand to be used is generally 1 to 2 times mol, preferably equimolar to 1 mol of the ruthenium-halide complex.
- solvent used in this reaction examples include aromatic hydrocarbons such as toluene and xylene, aromatic hydrocarbons such as benzene, toluene and xylene; aliphatic hydrocarbons such as pentane and hexane; dichloromethane, chloroform, Halogen hydrocarbons such as trichloromethane, carbon tetrachloride, 1,2-dichloroethane; ethers such as diethyl ether, tetrahydrofuran (THF), 1,2-dimethoxyethane, 1,4-dioxane; methanol, ethanol, n- Alcohols such as propanol, isopropanol, butanol, benzyl alcohol; N, N-dimethylformamide (DMF), N, N-dimethylacetamide, 1,3-dimethylimidazolidine, 1,3-dimethyl-2-imidazolide Non, N-methylpyrrolidone, he
- the amount of the solvent used is 1 ml to 100 ml with respect to 1 g of the substrate, preferably 1 ml to 10 ml with respect to 1 g of the substrate.
- the reaction temperature is usually in the range of 0 to 200 ° C, preferably room temperature to 100 ° C.
- the resulting phosphine-ruthenium-halide complex can be reacted with a diamine compound to obtain a corresponding amine-phosphine-ruthenium-halide complex.
- the amount of the diamine compound used for this reaction is usually 1 to 2 moles, preferably equimolar to the phosphine-ruthenium-halide complex.
- the reaction temperature is usually in the range of ⁇ 100 to 200 ° C., preferably ⁇ 10 to 50 ° C.
- An amine-phosphine-ruthenium-halide complex can also be obtained by allowing a diamine compound to act on a phosphine-ruthenium-halide complex isolated in advance under the same conditions as described above.
- the ruthenium compound represented by the formula (I) produced as described above is useful as an asymmetric reduction catalyst for a carbonyl compound, particularly an ⁇ -aminoketone compound represented by the formula (IV).
- Asymmetric reduction reaction of ⁇ -aminoketone compound The above-mentioned ruthenium compound can be produced by asymmetric reduction (hydrogenation) of a carbonyl compound to produce an optically active alcohol compound.
- it is suitable for producing an optically active amino alcohol compound such as an ephedrine compound by asymmetric reduction (hydrogenation) of an ⁇ -amino ketone compound.
- an asymmetric reduction reaction is demonstrated.
- the ⁇ -aminoketone compound serving as a substrate for the asymmetric reduction reaction is not particularly limited as long as it has a structure capable of performing the asymmetric reduction reaction, but preferably the formula (IV) (Wherein R 10 and R 11 are each independently a C1-6 alkyl group having an unsubstituted or substituted group or a C6-18 aryl group having an unsubstituted or substituted group, and R 12 and R 13 are A hydrogen atom, an unsubstituted or substituted C1-6 alkyl group, an unsubstituted or substituted C6-18 aryl group, an R 14 CO— group or an R 14 OCO— group, wherein R 14 is unsubstituted or Represents a C1-6 alkyl group having a substituent, a C6-18 aryl group having no substituent or a substituent, and R 10 and R 11 and R 12 and R 13 may be bonded to each other to form a ring; ).
- C1-6 alkyl group of “unsubstituted or substituted C1-6 alkyl group” means methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, t-butyl, Including butyl, n-pentyl, isopentyl, neopentyl, t-pentyl, hexyl and the like.
- the “unsubstituted or substituted C6-18 aryl group” is a monocyclic or polycyclic aryl group. In the case of a polycyclic aryl group, a partially saturated group is included in addition to the fully unsaturated group. Examples include phenyl, naphthyl, azulenyl, indenyl, indanyl, tetralinyl and the like. Preferably, it is a C6-10 aryl group.
- R 14 of "R 14 CO- group or R 14 OCO- group” represents an unsubstituted or C1 ⁇ 6 alkyl group having a substituent, C6 ⁇ 18 aryl group with an unsubstituted or substituted group, "C1 ⁇ 6
- the “alkyl group” and the “C6-18 aryl group” include the same groups as described above.
- the “R 14 CO— group” includes C1-6 alkylcarbonyl groups such as acetyl, propionyl, butyryl, pivaloyl, and arylcarbonyl groups such as benzoyl.
- the “R 14 OCO— group” includes C1-6 alkyloxycarbonyl groups such as methyloxycarbonyl, ethyloxycarbonyl, hexyloxycarbonyl, and aryloxycarbonyl groups such as phenyloxycarbonyl, 1-naphthyloxycarbonyl and the like.
- the “substituent” of “unsubstituted or substituted” includes the same groups as the “substituent” of “unsubstituted or substituted” in the ruthenium compound represented by the formula (I).
- R 10 and R 11 and R 12 and R 13 may be bonded to each other to form a ring” means that R 10 and R 11 are bonded to form a hydrocarbon ring such as an alkyl ring or an alkenyl ring. When formed, and / or R 12 and R 13 may combine to form a heterocycle such as a nitrogen-containing hydrocarbon ring.
- the ⁇ -aminoketone compound as a substrate is asymmetrically reduced in the presence of hydrogen gas or a hydrogen donor at a predetermined pressure by optionally adding a base in the presence of the ruthenium compound represented by the formula (I). To do.
- a ruthenium complex (or ruthenium salt), a phosphorus compound and a diamine compound, which are raw materials for the ruthenium compound, are separately added to the reaction system, or a ruthenium complex (or ruthenium salt) having a phosphine ligand and
- the amount of the ruthenium compound represented by the formula (I) used as a catalyst varies depending on the size of the reaction vessel and the catalytic activity, but is usually 1/50 to 1/2 of the ⁇ -aminoketone compound as the reaction substrate.
- the range is 1,000,000 times mole, preferably 1/500 to 1 / 500,000 times mole.
- Examples of the base used include organic bases such as triethylamine, diisopropylethylamine, pyridine, DABCO and DBU; metal alkoxides such as sodium methoxide, sodium ethoxide, potassium t-butoxide, magnesium methoxide and magnesium ethoxide; n Organic lithium compounds such as butyl lithium; lithium amides such as LDA and lithium bistrimethylsilylamide; alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide; alkalis such as magnesium hydroxide and calcium hydroxide Earth metal hydroxides; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkali metal hydrogen carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate; alkaline earth such as magnesium carbonate and calcium carbonate Metal carbonate; sodium hydride, metal hydrides such as calcium hydride; and the like.
- the amount of the base to be added is usually 2 to 500,000 times mol, preferably 2 to 5,000 times
- the solvent is not particularly limited as long as it can solubilize the substrate and the catalyst.
- Specific examples thereof include alcohols such as methanol, ethanol, n-propanol, isopropanol, butanol and benzyl alcohol; aromatic hydrocarbons such as benzene, toluene and xylene; aliphatic hydrocarbons such as pentane and hexane; dichloromethane Halogen hydrocarbons such as chloroform, trichloromethane, carbon tetrachloride, 1,2-dichloroethane; ethers such as diethyl ether, THF, 1,2-dimethoxyethane, 1,4-dioxane; DMF, N, N— Amides such as dimethylacetamide, 1,3-dimethylimidazolidine, 1,3-dimethyl-2-imidazolidinone, N-methylpyrrolidone and HMPT; nitriles such as acetonitrile
- solvents can be used alone or in admixture of two or more.
- the use of alcohols is preferred because the reaction product is an alcohol compound.
- the amount of solvent used depends on the solubility and economics of the ⁇ -aminoketone compound, and in some cases, the reaction proceeds even in the absence of a solvent or close to high dilution conditions, but is usually based on 100 parts by weight of the ⁇ -aminoketone compound.
- the range is 0.1 to 10,000 parts by weight, preferably 20 to 1,000 parts by weight.
- the hydrogen pressure is usually in the range of 1 to 200 atm, preferably 3 to 50 atm.
- the hydrogen donor for example, a hydrogen storage alloy or diimide can be used. It is usually in the range of 1 to 100 times equivalent to the aminoketone compound.
- the reaction temperature is usually in the temperature range of ⁇ 50 to 100 ° C., preferably 25 to 40 ° C.
- the reaction time depends on the reaction conditions such as the reaction substrate concentration, temperature, and pressure, but is usually from several minutes to several days. Although there is no restriction
- the desired product can be obtained by isolation and purification by ordinary organic synthetic chemical techniques.
- the structure of the target product can be determined by known analytical means such as 1 H-NMR, optical rotation measurement, liquid chromatography, gas chromatography and the like.
- Example 1 Synthesis of Ruthenium Compound (Example 1-1) ⁇ (S) -6,6'-bis [bis- (3,5-dimethyl-phenyl) -phosphanyl] -2,2'-dimethyl-biphenyl ⁇ ruthenium (II) dichloride (2S) -1,1-bis Synthesis of (4-methoxyphenyl) -2-isopropyl 1,2-ethanediamine complex Dichloromethane (3 ml), ⁇ (S) -6,6′-bis [bis- (3,5-dimethyl-phenyl) -phosphanyl] -2,2′-dimethyl-biphenyl ⁇ ruthenium (3 ml) deaerated in a Schlenk tube II) Dichloride DMF adduct (147 mg, 150 ⁇ mol) and (2S) -1,1-bis (4-methoxyphenyl) -2-isopropylethane-1,2-diamine (52 mg,
- Example 1-2 ⁇ (S) -6,6'-bis [bis- (3,5-dimethyl-phenyl) -phosphanyl] -2,2'-dimethyl-biphenyl ⁇ ruthenium (II) dichloride (1S, 2S) -1,2 -Diphenyl) -1,2-ethanediamine complex synthesis (2S) -1,1-bis (4-methoxyphenyl) -2-isopropylethane-1,2-diamine instead of (1S, 2S) -1, ⁇ (S) -6,6′-bis [bis- (3,5-dimethyl-phenyl) -phosphanyl] was prepared in the same manner as in Example 1-1 except that 2-diphenyl-1,2-ethanediamine was used.
- Example 2 Synthesis of (1S, 2S) -1-phenyl-2- (N-methyl-N-benzoylamino) -1-propanol
- Example 2-2 The target product was obtained in the same manner as in Example 2-1, except that S / C was 10,000.
- S / C 10,000
- Example 2-3 Other than using (1S, 2S) -1,2-diphenyl-1,2-ethanediamine instead of (2S) -1,1-bis (4-methoxyphenyl) -2-isopropylethane-1,2-diamine Obtained the desired product in the same manner as in Example 2-1.
- S / C 1,000 Initial hydrogen pressure: 1 MPa Reaction time: 16 hours Conversion: 100% syn: anti:> 20: 1 Enantiomeric excess: 95% ee
- Example 2-5 As a Ru complex, ⁇ (S) -6,6′-bis [bis- (3,5-dimethyl-phenyl) -phosphanyl] -2,2′-dimethyl-biphenyl ⁇ ruthenium (II) dichloride (1S, 2S) — The target product was obtained in the same manner as in Example 2-1, except that 1,2-diphenyl) -1,2-ethanediamine complex was used. Conversion rate: 100% syn: anti:> 20: 1 Enantiomeric excess: 95% ee
- Example 2-6 As a Ru complex, ⁇ (S) -6,6′-bis [bis- (3,5-dimethyl-phenyl) -phosphanyl] -2,2′-dimethyl-biphenyl ⁇ ruthenium (II) dichloride (1S, 2S) — The product of interest was obtained in the same manner as in Example 2-4 except that 1,2-diphenyl-1,2-ethanediamine complex was used (isolation yield 98%). S / C: 1,000 Conversion rate: 100% syn: anti:> 20: 1 (NMR) Enantiomeric excess: 95% ee
- Example 2--7 (S) -1,1′-binaphthyl-2,2′-bis- [di- (3,5-xylyl)] phosphine ruthenium (II) dichloride (2S) -1,1-bis (4-methoxyphenyl)
- the target product was obtained in the same manner as in Example 2-4 except that -2-isopropyl-1,2-ethanediamine complex was used.
- Example 2-10 (S) -4,4′-bi-1,3-benzodioxole-5,5′-diyl-bis [di (3,5-xylyl) phosphine] ruthenium (II) dichloride (2S) -1,
- the target product was obtained in the same manner as in Example 2-4 except that 1-bis (4-methoxyphenyl) -2-isopropyl-1,2-ethanediamine complex was used.
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Abstract
Description
本願は、2008年4月7日に、日本に出願された特願2008-099267号に基づき優先権を主張し、その内容をここに援用する。
従って、水素ガス等の安価な水素源を用いて、カルボニル化合物から対応する光学活性アルコール化合物を高選択的、高収率で製造できる、安価な不斉水素化触媒の開発が望まれていた。
Pxはホスフィン配位子を表し、nは1又は2を表す。
Aは、下記に示す式(4)又は式(5)で表されるジアミン配位子を表す。
(1)式(I)
〔式中、Xは、ハロゲン原子を表す。
Pxxは、式(II)
[式中、R5は、式(III)
(式中、Raは、水素原子、ハロゲン原子、C1~6アルキル基、C1~6アルコキシ基又はC6~18アリール基を、Rbは、ハロゲン原子、C1~6アルキル基、C1~6アルコキシ基又はC6~18アリール基を表す。)で表される置換基を有するフェニル基を表す。Aは、2価の有機基を表す。]で表される光学活性2座ホスフィン配位子を表す。R1R2C(NH2)-R3R4C(NH2)は、光学活性ジアミン配位子を表す。R1~R4はそれぞれ独立して、水素原子、無置換若しくは置換基を有するC1~20アルキル基、無置換若しくは置換基を有するC2~20アルケニル基、無置換若しくは置換基を有するC3~8シクロアルキル基、無置換若しくは置換基を有するC4~8シクロアルケニル基、無置換若しくは置換基を有するC6~18アリール基又は無置換若しくは置換基を有するC7~18アラルキル基を表し、R1とR2のいずれかがR3とR4のいずれかと結合して環を形成してもよい。〕で表されるルテニウム化合物、及び
(2)上記ルテニウム化合物の存在下、α-アミノケトン化合物、特に、式(IV)
(式中、R10及びR11は、それぞれ独立して、無置換若しくは置換基を有するC1~6アルキル基又は無置換若しくは置換基を有するC6~18アリール基であり、R12及びR13は水素原子、無置換若しくは置換基を有するC1~6アルキル基、無置換若しくは置換基を有するC6~18アリール基、R14CO-基又はR14OCO-基を表す。R14は、無置換若しくは置換基を有するC1~6アルキル基又は無置換若しくは置換基を有するC6~18アリール基を表す。R10とR11及びR12とR13は、それぞれ、結合して環を形成してもよい。)で表されるα-アミノケトン化合物を水素化することを特徴とする光学活性アミノアルコール化合物の製造方法に関する。
(3)上記式(IV)中、R10が、無置換若しくは置換基を有するフェニル基であることを特徴とする(2)に記載の光学活性アミノアルコール化合物の製造方法であり、
(4)上記式(I)で表されるルテニウム化合物において、式(II)で表される光学活性2座ホスフィン配位子が、式(II-B)
(式中、R5は、上記と同じ意味を表す。)で表される光学活性2座ホスフィン配位子、式(II-C)
(式中、R5は、上記と同じ意味を表す。)で表される光学活性2座ホスフィン配位子、式(II-D)
(式中、R5は、上記と同じ意味を表す。)で表される光学活性2座ホスフィン配位子、式(II-E)
(式中、R5は上記と同様の意味を表す。Rd は、C1~6アルキル基、C1~6アルコキシ基、ハロゲン原子又はトリフルオロメチル基を表す。Re は、水素原子、C1~6アルキル基、C1~6アルコキシ基又はハロゲン原子を表す。Rfは、水素原子、C1~6アルキル基又はC1~6アルコキシ基を表す。)で表される光学活性2座ホスフィン配位子、式(II-F)
(式中、R5は上記と同様の意味を表す。Rg は、水素原子又は無置換若しくは置換基を有するC1~6アルキル基を表す。Rh は、水素原子又は無置換若しくは置換基を有するC1~6アルキル基を表す。)で表される光学活性2座ホスフィン配位子、又は、式(II-G)
(式中、R5は上記と同様の意味を表す。Ri 及びRjは、それぞれ独立して、無置換若しくは置換基を有するC1~6アルキル基又は無置換若しくは置換基を有するC6~18アリール基を表す。Ri とRjは、結合して環を形成してもよい。Bは、単結合又は無置換若しくは置換基を有するC1~6アルキレン基を表す。)で表される光学活性2座ホスフィン配位子のいずれかであることを特徴とする(2)又は(3)に記載の光学活性アミノアルコール化合物の製造方法であり、
(5)上記式(I)で表されるルテニウム化合物において、式(II)で表される光学活性2座ホスフィン配位子が、式(II-A)
(式中、Rcは、C1~6アルキル基、C1~6アルコキシ基、ハロゲン原子又はトリフルオロメチル基を表す。R5は、上記と同じ意味を表す。)で表される光学活性2座ホスフィン配位子であることを特徴とする(2)又は(3)に記載の光学活性アミノアルコール化合物の製造方法であり、
(6)上記式(II-A)で表される光学活性2座ホスフィン配位子が、2,2’-ビス[ビス(3,5-ジメチルフェニル)ホスファニル]-6,6’-ジメチル-1,1’-ビフェニルであることを特徴とする(5)に記載の光学活性アミノアルコール化合物の製造方法であり、
(7)上記式(I)で表されるルテニウム化合物において、光学活性ジアミン配位子が、1,1-ビス(4-メトキシフェニル)-2-イソプロピル-1,2-エタンジアミン、1,2-ジフェニル-1,2-エタンジアミン、又は1,2-ジアミノシクロヘキサンであることを特徴とする(2)~(6)のいずれかに記載の光学活性アミノアルコール化合物の製造方法である。
(8)式(I-A)
〔式中、Xは、ハロゲン原子を表す。
Paxxは、式(II-A)
[式中、Rcは、C1~6アルキル基、C1~6アルコキシ基、ハロゲン原子又はトリフルオロメチル基を表す。R5は、式(III)
(式中、Raは、水素原子、ハロゲン原子、C1~6アルキル基、C1~6アルコキシ基又はC6~18アリール基を、Rbは、ハロゲン原子、C1~6アルキル基、C1~6アルコキシ基又はC6~18アリール基を表す。)で表される置換基を有するフェニル基を表す。]で表される光学活性2座ホスフィン配位子を表す。R1R2C(NH2)-R3R4C(NH2)は、光学活性ジアミン配位子を表す。R1~R4はそれぞれ独立して、水素原子、無置換若しくは置換基を有するC1~20アルキル基、無置換若しくは置換基を有するC2~20アルケニル基、無置換若しくは置換基を有するC3~8シクロアルキル基、無置換若しくは置換基を有するC4~8シクロアルケニル基、無置換若しくは置換基を有するC6~18アリール基又は無置換若しくは置換基を有するC7~18アラルキル基を表し、R1とR2のいずれかがR3とR4のいずれかと結合して環を形成してもよい。〕で表されるルテニウム化合物であり、
(9)上記式(I-A)で表されるルテニウム化合物において、式(II-A)で表される光学活性2座ホスフィン配位子が、2,2’-ビス[ビス(3,5-ジメチルフェニル)ホスファニル]-6,6’-ジメチル-1,1’-ビフェニルであることを特徴とする(8)に記載のルテニウム化合物であり、
(10)上記式(I-A)で表されるルテニウム化合物において、光学活性ジアミン配位子が、1,1-ビス(4-メトキシフェニル)-2-イソプロピル-1,2-エタンジアミン、1,2-ジフェニル-1,2-エタンジアミン、又は1,2-ジアミノシクロヘキサンであることを特徴とする(8)又は(9)に記載のルテニウム化合物である。
本発明のルテニウム化合物は、実施例に示したように、α-アミノケトン類から光学活性アミノアルコール化合物を高立体選択的、かつ高収率に製造することができる。
(1)ルテニウム化合物
本発明の式(I)で表される化合物について以下に詳述する。
下記式(I)
において、
Xは、「ハロゲン原子」であり、フッ素、塩素、臭素、ヨウ素等を表す。 Pxxは、式(II)
で表される光学活性2座ホスフィン配位子を表す。
で表される置換基を有するフェニル基を表す。式中、Raは、水素原子、ハロゲン原子、C1~6アルキル基、C1~6アルコキシ基又はC6~18アリール基を、Rbは、ハロゲン原子、C1~6アルキル基、C1~6アルコキシ基又はC6~18アリール基を表す。
「C1~8アルキレン基」は、メチレン、エチレン、トリメチレン等を包含する。
「ハロゲン原子」は、フッ素、塩素、臭素、ヨウ素等を表す。
「C1~6アルキル基」は、メチル、エチル、n-プロピル、イソプロピル、n-ブチル、sec-ブチル、t-ブチル、n-ペンチル、イソペンチル、ネオペンチル、t-ペンチル、ヘキシル等を包含する。
「C1~6アルコキシ基」は、メトキシ、エトキシ、n-プロポキシ、イソプロポキシ、n-ブトキシ、sec-ブトキシ、t-ブトキシ等を包含する。
「C6~18アリール基」は、単環又は多環のC6~18アリール基であり、多環アリール基の場合は、完全不飽和に加え、部分飽和の基も包含する。例えばフェニル、ナフチル、アズレニル、インデニル、インダニル、テトラリニル等を包含する。好ましくは、C6~10アリール基である。
(式中、R5は、式(III)
(式中、Raは、水素原子、ハロゲン原子、C1~6アルキル基、C1~6アルコキシ基又はC6~18アリール基を、Rbは、ハロゲン原子、C1~6アルキル基、C1~6アルコキシ基又はC6~18アリール基を表す。)で表される置換基を有するフェニル基を表す。)で表されるホスフィン配位子を挙げることができる。R5 は、好ましくは、3,5-ジメチルフェニル基である。
(式中、R5は上記と同様の意味を表す。)で表されるホスフィン配位子を挙げることができる。R5 は、好ましくは、3,5-ジメチルフェニル基である。
(式中、R5は上記と同様の意味を表す。)で表されるホスフィン配位子を挙げることができる。R5 は、好ましくは、3,5-ジメチルフェニル基である。
(式中、R5は上記と同様の意味を表す。Rd は、C1~6アルキル基、C1~6アルコキシ基、ハロゲン原子、トリフルオロメチル基を表す。Re は、水素原子、C1~6アルキル基、C1~6アルコキシ基、ハロゲン原子を表す。Rf は、水素原子、C1~6アルキル基、C1~6アルコキシ基を表す。)で表されるホスフィン配位子を挙げることができる。Rd、Re及びRfの「C1~6アルキル基」、「C1~6アルコキシ基」の具体例は、式(III)で例示した置換基と同様の置換基を例示することができる。
具体的には、(4,4’,6,6’-テトラメチル-5,5’-ジメトキシビフェニル-2,2’-ジイル)-ビス(ビス(3,5-ジメチルフェニル)ホスフィン)、(4,4’,6,6’-テトラトリフルオロメチルビフェニル-2,2’-ジイル)-ビス(ビス(3,5-ジメチルフェニル)ホスフィン)、(4,6-ジトリフロロメチル-4’,6’-ジメチル-5’-メトキシビフェニル-2,2’-ジイル)-ビス(ビス(3,5-ジメチルフェニル)ホスフィン)、(4,4’,5,5’,6,6’-テトラヘキサメトキシビフェニル-2,2’-ジイル)-ビス(ビス(3,5-ジメチルフェニル)ホスフィン)が挙げられる。
(式中、R5は上記と同様の意味を表す。Rc は、C1~6アルキル基、C1~6アルコキシ基、ハロゲン原子、トリフルオロメチル基を表す。)で表されるホスフィン配位子を挙げることができる。Rcの「C1~6アルキル基」の具体例は、式(III)で例示した置換基と同様の置換基を例示することができる。R5 は、好ましくは、3,5-ジメチルフェニル基である。
具体的には、2,2’-ビス[ビス(3,5-ジメチルフェニル)ホスファニル]-6,6’-ジメチル-1,1’-ビフェニル、2,2’-ビス[ビス(3,5-ジメチルフェニル)ホスファニル]-6,6’-ジメトキシ-1,1’-ビフェニル、2,2’-ビス[ビス(3,5-ジメチルフェニル)ホスファニル]-6,6’-ジクロロ-1,1’-ビフェニルが挙げられる。
(式中、R5は上記と同様の意味を表す。Rg は、水素原子又は無置換若しくは置換基を有するC1~6アルキル基を表す。Rh は、水素原子又は無置換若しくは置換基を有するC1~6アルキル基を表す。)で表される光学活性2座ホスフィン配位子を挙げることができる。Rg及びRhの「C1~6アルキル基」の具体例は、式(III)で例示した置換基と同様の置換基を例示することができる。R5 は、好ましくは、3,5-ジメチルフェニル基である。
具体的には、1’,2-ビス[ビス(3,5-ジメチルフェニル)ホスフィノ]フェロセニルエタンが挙げられる。
(式中、R5は上記と同様の意味を表す。Ri 及びRjは、それぞれ独立して、無置換若しくは置換基を有するC1~6アルキル基又は無置換若しくは置換基を有するC6~18アリール基を表す。Ri とRjは、結合して環を形成してもよい。Bは、単結合又は無置換若しくは置換基を有するC1~6アルキレン基を表す。)で表される光学活性2座ホスフィン配位子を挙げることができる。Ri及びRjの「C1~6アルキル基」、「C6~18アリール基」の具体例は、式(III)で例示した置換基と同様の置換基を例示することができる。「C1~6アルキレン基」は、メチレン、エチレン、トリメチレン等を包含する。R5 は、好ましくは、3,5-ジメチルフェニル基である。
具体的には、2,3-ビス(ビス(3,5-ジメチルフェニル)ホスフィノ)ブタン、1,2-ビス(ビス(3,5-ジメチルフェニル)ホスフイノ)プロパン、5,6-ビス(ビス(3,5-ジメチルフェニル)ホスフィノ)-2-ノルボルネン、1-ベンゾイル-3,4-ビス(ビス(3,5-ジメチルフェニル)ホスフィノ)ピロリジン、2,4-ビス(ビス(3,5-ジメチルフェニル)ホスフィノ)ペンタン、2,3-o-イソブロピリデン-2,3-ジヒドロキシ-1,4-ビス(ビス(3,5-ジメチルフェニル)ホスフィノ)ブタンが挙げられる。
ジアミン配位子の具体例としては、以下の表に示す置換基の組合せからなる化合物を包含するが、これに限定されるものではない。なお、表中、略号は以下の意味を有する。
Ph:フェニル、c-Pr:シクロプロピル、c-He:シクロヘキシル
で表される。
Paxxは、上記式(II-A)で表される光学活性2座ホスフィン配位子を表す。X及びR1R2C(NH2)-R3R4C(NH2)は、上記と同様の意味を表す。
{(S)-6,6’-ビス[ビス-(3,5-ジメチル-フェニル)-ホスファニル]-2,2’-ジメチル-ビフェニル}ルテニウム(II)ジクロリド(2S)-1,1-ビス(4-メトキシフェニル)-2-イソプロピル1,2-エタンジアミン、{(S)-6,6’-ビス[ビス-(3,5-ジメチル-フェニル)-ホスファニル]-2,2’-ジメチル-ビフェニル}ルテニウム(II)ジクロリド(1S,2S)-1,2-ジフェニル)-1,2-エタンジアミン、{(S)-6,6’-ビス[ビス-(3,5-ジメチル-フェニル)-ホスファニル]-2,2’-ジメチル-ビフェニル}ルテニウム(II)ジクロリド(1S,2S)-1,2-ジアミノシクロへキサンなどを挙げることができる。
本発明のルテニウム化合物は、公知の方法により製造することができる(上記特許文献2、特許文献3などを参照)。
例えば、以下の方法により製造することができる。
ルテニウム化合物の製造方法に用いられる出発原料としては、0価、1価、2価、3価及び、さらに高原子価のルテニウムを用いることができる。これらの中でも、Angew.Chem.Int.Ed.,37,1703(1998)に記載の2価ルテニウム錯体を用いる方法が簡便である。すなわち、2価のルテニウム-ハライド錯体と2座ホスフィン配位子の溶媒溶液を加熱後、ジアミン化合物を加えることで式(I)で表されるルテニウム化合物を製造することができる。
まず、出発原料の2価のルテニウム-ハライド錯体と2座ホスフィン配位子とを、溶媒中、加熱し反応させ、対応するホスフィン-ルテニウム-ハライド錯体を得る。
出発原料の2価のルテニウム-ハライド錯体としては、2座ホスフィン配位子及びジアミン配位子と置換可能な配位子を有するルテニウム錯体であれば、特に制限されるものではない。その具体例としては、[2塩化ルテニウム(ノルボルナジエン)]多核体、[2塩化ルテニウム(シクロオクタジエン)]多核体、[ビス(メチルアリル)ルテニウム(シクロオクタジエン)]等のジエンが配位したハロゲン化ルテニウム化合物;[2塩化ルテニウム(ベンゼン)]二核体、[2塩化ルテニウム(p-シメン)]二核体、[2塩化ルテニウム(トリメチルベンゼン)]二核体、[2塩化ルテニウム(ヘキサメチルベンゼン)]二核体等の芳香族化合物が配位したハロゲン化ルテニウム;等が挙げられる。
2座ホスフィン配位子の使用量は、ルテニウム-ハライド錯体1モルに対して、通常1~2倍モル、好ましくは等モルである。
溶媒の使用量は、基質1gに対して1ml~100ml、好ましくは、基質1gに対し、1ml~10mlの範囲である。反応温度は、通常、0~200℃、好ましくは、室温~100℃の範囲である。
上記ルテニウム化合物は、カルボニル化合物を不斉還元(水素化)して光学活性アルコール化合物を製造することができる。特に、α-アミノケトン化合物を不斉還元(水素化)して光学活性アミノアルコール化合物、例えば、エフェドリン類化合物を製造するのに好適である。
以下に、不斉還元反応について説明する。
(式中、R10及びR11は、それぞれ独立して、無置換若しくは置換基を有するC1~6アルキル基又は無置換若しくは置換基を有するC6~18アリール基であり、R12及びR13は水素原子、無置換若しくは置換基を有するC1~6アルキル基、無置換若しくは置換基を有するC6~18アリール基、R14CO-基又はR14OCO-基を表す。R14は、無置換若しくは置換基を有するC1~6アルキル基、無置換若しくは置換基を有するC6~18アリール基を表す。R10とR11及びR12とR13は、それぞれ、結合して環を形成してもよい)で表される化合物である。
「R14CO-基又はR14OCO-基」のR14は、無置換若しくは置換基を有するC1~6アルキル基、無置換若しくは置換基を有するC6~18アリール基を表し、「C1~6アルキル基」及び「C6~18アリール基」は、上記と同様の基が包含される。
「R14OCO-基」は、メチルオキシカルボニル、エチルオキシカルボニル、ヘキシルオキシカルボニル等のC1~6アルキルオキシカルボニル基、フェニルオキシカルボニル、1-ナフチルオキシカルボニルなどのアリールオキシカルボニル基を包含する。
「無置換若しくは置換基を有する」の「置換基」は、式(I)で表されるルテニウム化合物における「無置換若しくは置換基を有する」の「置換基」と同様の基を包含する。
また、本発明においては、ルテニウム化合物の原料となるルテニウム錯体(又はルテニウム塩)、リン化合物及びジアミン化合物とを別々に反応系に添加、又はホスフィン配位子を有するルテニウム錯体(又はルテニウム塩)及びジアミン化合物とを別々に反応系に添加して、必要に応じて塩基を添加してルテニウム化合物を生成させた後、該ルテニウム化合物を反応系から取り出すことなく、そこへ基質を添加することにより、in situで不斉還元反応を行わせることもできる。
添加する塩基の量は、ルテニウム化合物に対し、通常2~500,000倍モル、好ましくは、2~5,000倍モルの範囲である。
溶媒の使用量は、α-アミノケトン化合物の溶解度及び経済性に依存し、場合によっては無溶媒又は高希釈条件に近い状態でも反応は進行するが、通常、α-アミノケトン化合物100重量部に対して0.1~10,000重量部、好ましくは20~1,000重量部の範囲である。
(1)JMTC-300(300MHz、日本電子社製)
(2)旋光度の測定:旋光度計、JASCO DIP-360(日本分光社製)
(3)高速液体クロマトグラフィー:LC-10Advp、SPD-10Avp(島津製作所社製)
(実施例1-1)
{(S)-6,6’-ビス[ビス-(3,5-ジメチル-フェニル)-ホスファニル]-2,2’-ジメチル-ビフェニル}ルテニウム(II)ジクロリド(2S)-1,1-ビス(4~メトキシフェニル)~2-イソプロピル1,2-エタンジアミン錯体の合成
シュレンクチューブ中に脱気したジクロロメタン (3ml), {(S)-6,6’-ビス[ビス-(3,5-ジメチル-フェニル)-ホスファニル]-2,2’-ジメチル-ビフェニル}ルテニウム(II)ジクロリド DMF付加体 (147mg, 150μmol) 及び (2S)-1,1-ビス(4-メトキシフェニル)-2-イソプロピルエタン-1,2-ジアミン (52mg, 165μmol) を加え室温にて3時間攪拌後、溶媒を留去した。シリカゲルショートカラム(溶出液:ジエチルエーテル)で精製し目的物(128mg,74%) を得た。
31P-NMR (CDCl3) d43.4 (d, Jp-p=35.9 Hz), 46.6 (d, Jp-p=35.9 Hz).
[a]D 29=-175°(c=1.01,CHCl3)
{(S)-6,6’-ビス[ビス-(3,5-ジメチル-フェニル)-ホスファニル]-2,2’-ジメチル-ビフェニル}ルテニウム(II)ジクロリド(1S,2S)-1,2-ジフェニル)-1,2-エタンジアミン錯体の合成
(2S)-1,1-ビス(4-メトキシフェニル)-2-イソプロピルエタン-1,2-ジアミンの替わりに(1S,2S)-1,2-ジフェニル-1,2-エタンジアミンを用いる以外は、実施例1-1と同様の方法で{(S)-6,6’-ビス[ビス-(3,5-ジメチル-フェニル)-ホスファニル]-2,2’-ジメチル-ビフェニル}ルテニウム(II)ジクロリド DMF付加体(91.8mg,94μmol) および(1S,2S)-1,2-ジフェニル-1,2-エタンジアミン (22mg,104μmmol) から目的物(71.2mg,72%) を得た。
31P-NMR (CDCl3) d44.8.
[a]D 29=-143°(c=1.01,CHCl3)
(実施例2-1)
Ar雰囲気下、100mlオートクレーブ中に1-フェニル-2-(N-メチル-N-ベンゾイル)アミノプロパン-1-オン(534mg,2mmol), {(S)-6,6’-ビス[ビス-(3,5-ジメチル-フェニル)-ホスファニル]-2,2’-ジメチル-ビフェニル}ルテニウム(II)ジクロリド DMF付加体 (2mg,2μmol,S/C=1,000), (2S)-1,1-ビス(4-メトキシフェニル)-2-イソプロピルエタン-1,2-ジアミン(0.8mg,2.5μmol)および2-プロパノール(2ml) を加え30分攪拌した後、tBuOK (1M 2-プロパノール溶液, 60μl, 60μmol) を加え水素を1MPaまで圧入した。25 ℃にて16時間攪拌した後、反応混合物を濃縮し粗生成物の1H-NMRを測定したところ、原料は全て消費されており、得られた(1S, 2S)-1-フェニル-2-(N-メチル-N-ベンゾイルアミノ)-1-プロパノールのジアステレオマ-比はsyn:anti >20:1 (anti体のシグナルは観測されない) であった。シリカゲルカラムクロマトグラフィー(溶離液:ヘキサン/酢酸エチル=1/1,1/2)で精製し、表題化合物509mg (95%)を得た。鏡像異性体過剰率はHPLC (カラム:ダイセル キラルパック OJ-H) で決定し>99%eeであった。
S/C=10,000とした以外は、実施例2-1と同様の方法で、目的物を得た。
S/C:10,000
水素初期圧:6MPa
反応時間:16時間
転化率:100%
syn:anti:>20:1
鏡像体過剰率:99%ee
(2S)-1,1-ビス(4-メトキシフェニル)-2-イソプロピルエタン-1,2-ジアミンに換えて(1S,2S)-1,2-ジフェニル-1,2-エタンジアミンを用いる以外は、実施例2-1と同様の方法で目的物を得た。
S/C:1,000
水素初期圧:1MPa
反応時間:16時間
転化率:100%
syn:anti:>20:1
鏡像体過剰率:95%ee
Ar雰囲気下、100mlオートクレーブ中に1-フェニル-2-(N-メチル-N-ベンゾイル)アミノプロパン-1-オン(534mg,2mmol), {(S)-6,6’-ビス[ビス-(3,5-ジメチル-フェニル)-ホスファニル]-2,2’-ジメチル-ビフェニル}ルテニウム(II)ジクロリド(2S)-1,1-ビス(4-メトキシフェニル)-2-イソプロピル1,2-エタンジアミン錯体(2mg、2μmol,S/C=1,000), 2-プロパノール(2ml) 及びtBuOK (1M 2-プロパノール溶液, 60μl,60μmol) を加えた後、水素を1MPaまで圧入し25 ℃にて16時間攪拌した。目的物の精製及び分析は実施例2-1と同様の方法で行った (単離収率99%)。
転化率:100%
syn:anti:>20:1
鏡像体過剰率:>99%ee
Ru錯体として {(S)-6,6’-ビス[ビス-(3,5-ジメチル-フェニル)-ホスファニル]-2,2’-ジメチル-ビフェニル}ルテニウム(II)ジクロリド(1S,2S)-1,2-ジフェニル)-1,2-エタンジアミン錯体を用いる以外は、実施例2-1と同様の方法で目的物を得た。
転化率:100%
syn:anti:>20:1
鏡像体過剰率:95%ee
Ru錯体として {(S)-6,6’-ビス[ビス-(3,5-ジメチル-フェニル)-ホスファニル]-2,2’-ジメチル-ビフェニル}ルテニウム(II)ジクロリド(1S,2S)-1,2-ジフェニル-1,2-エタンジアミン錯体を用いる以外は、実施例2-4と同様の方法で目的物を得た(単離収率98%)。
S/C:1,000
転化率:100%
syn:anti:>20:1(NMR)
鏡像体過剰率:95%ee
(S)-1,1’-ビナフチル-2,2’- ビス-[ジ-(3,5-キシリル)]ホスフィンルテニウム(II)ジクロリド(2S)-1,1-ビス(4-メトキシフェニル)-2-イソプロピル-1,2-エタンジアミン錯体を用いる以外は、実施例2-4と同様の方法で目的物を得た。
((S)-1,1’-ビナフチル-2,2’- ビス-[ジ-(3,5-キシリル)]ホスフィン:略称として(S)-XylBINAP)
S/C:1,000
水素初期圧:1.2MPa
反応時間:16時間
転化率:100%
syn:anti:>99:1(HPLC)
鏡像体過剰率:>99%ee
(S)-1,1’-ビナフチル-2,2’- ビス-[ジ-(3,5-キシリル)]ホスフィンルテニウム(II)ジクロリド(1S,2S)-1,2-ジフェニル-1,2-エタンジアミン錯体を用いる以外は、実施例2-4と同様の方法で目的物を得た(単離収率94%)。
S/C:1,000
水素初期圧:1.2MPa
反応時間:16時間
転化率:100%
syn:anti:>99:1(HPLC)
鏡像体過剰率:98%ee
S/C=5,000とし、(S)-6,6’-ジメチル-1,1’-ビナフチル-2,2’- ビス-[ジ-(3,5-キシリル)]ホスフィンルテニウム(II)ジクロリド(2S)-1,1-ビス(4-メトキシフェニル)-2-イソプロピル-1,2-エタンジアミン錯体を用いる以外は、実施例2-4と同様の方法で目的物を得た。
S/C:5,000
水素初期圧:1.2MPa
反応時間:1.5時間
転化率:100%
syn:anti:>99:1(HPLC)
鏡像体過剰率:>99%ee
(S)-4,4’-ビ-1,3-ベンゾジオキソール-5,5’-ジイル-ビス[ジ(3,5-キシリル) ホスフィン]ルテニウム(II)ジクロリド(2S)-1,1-ビス(4-メトキシフェニル)-2-イソプロピル-1,2-エタンジアミン錯体を用いる以外は、実施例2-4と同様の方法で目的物を得た。
((S)-4,4’-ビ-1,3-ベンゾジオキソール-5,5’-ジイル-ビス[ジ(3,5-キシリル) ホスフィン]:略称として(S)-XylSEGPHOS)
S/C:1,000
水素初期圧:1MPa
反応時間:16時間
転化率:100%
syn:anti:>20:1(NMR)
鏡像体過剰率:>99%ee
Claims (9)
- 式(I)
〔式中、Xは、ハロゲン原子を表す。
Pxxは、式(II)
[式中、R5は、式(III)
(式中、Raは、水素原子、ハロゲン原子、C1~6アルキル基、C1~6アルコキシ基又はC6~18アリール基を、Rbは、ハロゲン原子、C1~6アルキル基、C1~6アルコキシ基又はC6~18アリール基を表す。)で表される置換基を有するフェニル基を表す。Aは、2価の有機基を表す。]で表される光学活性2座ホスフィン配位子を表す。R1R2C(NH2)-R3R4C(NH2)は、光学活性ジアミン配位子を表す。R1~R4はそれぞれ独立して、水素原子、無置換若しくは置換基を有するC1~20アルキル基、無置換若しくは置換基を有するC2~20アルケニル基、無置換若しくは置換基を有するC3~8シクロアルキル基、無置換若しくは置換基を有するC4~8シクロアルケニル基、無置換若しくは置換基を有するC6~18アリール基又は無置換若しくは置換基を有するC7~18アラルキル基を表し、R1とR2のいずれかがR3とR4のいずれかと結合して環を形成してもよい。〕で表されるルテニウム化合物の存在下、式(IV)
(式中、R10及びR11は、それぞれ独立して、無置換若しくは置換基を有するC1~6アルキル基又は無置換若しくは置換基を有するC6~18アリール基であり、R12及びR13は水素原子、無置換若しくは置換基を有するC1~6アルキル基、無置換若しくは置換基を有するC6~18アリール基、R14CO-基又はR14OCO-基を表す。R14は、無置換若しくは置換基を有するC1~6アルキル基又は無置換若しくは置換基を有するC6~18アリール基を表す。R10とR11及びR12とR13は、それぞれ、結合して環を形成してもよい。)で表されるα-アミノケトン化合物を水素化することを特徴とする光学活性アミノアルコール化合物の製造方法。 - 式(IV)中、R10が、無置換若しくは置換基を有するフェニル基であることを特徴とする請求項1に記載の光学活性アミノアルコール化合物の製造方法。
- 式(I)で表されるルテニウム化合物において、式(II)で表される光学活性2座ホスフィン配位子が、式(II-B)
(式中、R5は、上記と同じ意味を表す。)で表される光学活性2座ホスフィン配位子、式(II-C)
(式中、R5は、上記と同じ意味を表す。)で表される光学活性2座ホスフィン配位子、式(II-D)
(式中、R5は、上記と同じ意味を表す。)で表される光学活性2座ホスフィン配位子、式(II-E)
(式中、R5は上記と同様の意味を表す。Rd は、C1~6アルキル基、C1~6アルコキシ基、ハロゲン原子又はトリフルオロメチル基を表す。Re は、水素原子、C1~6アルキル基、C1~6アルコキシ基又はハロゲン原子を表す。Rfは、水素原子、C1~6アルキル基又はC1~6アルコキシ基を表す。)で表される光学活性2座ホスフィン配位子、式(II-F)
(式中、R5は上記と同様の意味を表す。Rg は、水素原子又は無置換若しくは置換基を有するC1~6アルキル基を表す。Rh は、水素原子又は無置換若しくは置換基を有するC1~6アルキル基を表す。)で表される光学活性2座ホスフィン配位子、又は、式(II-G)
(式中、R5は上記と同様の意味を表す。Ri 及びRjは、それぞれ独立して、無置換若しくは置換基を有するC1~6アルキル基又は無置換若しくは置換基を有するC6~18アリール基を表す。Ri とRjは、結合して環を形成してもよい。Bは、単結合又は無置換若しくは置換基を有するC1~6アルキレン基を表す。)で表される光学活性2座ホスフィン配位子のいずれかであることを特徴とする請求項1又は2に記載の光学活性アミノアルコール化合物の製造方法。 - 式(II-A)で表される光学活性2座ホスフィン配位子が、2,2’-ビス[ビス(3,5-ジメチルフェニル)ホスファニル]-6,6’-ジメチル-1,1’-ビフェニルであることを特徴とする請求項4に記載の光学活性アミノアルコール化合物の製造方法。
- 式(I)で表されるルテニウム化合物において、光学活性ジアミン配位子が、1,1-ビス(4-メトキシフェニル)-2-イソプロピル-1,2-エタンジアミン、1,2-ジフェニル-1,2-エタンジアミン、又は1,2-ジアミノシクロヘキサンであることを特徴とする請求項1~5のいずれかに記載の光学活性アミノアルコール化合物の製造方法。
- 式(I-A)
〔式中、Xは、ハロゲン原子を表す。
Paxxは、式(II-A)
[式中、Rcは、C1~6アルキル基、C1~6アルコキシ基、ハロゲン原子又はトリフルオロメチル基を表す。R5は、式(III)
(式中、Raは、水素原子、ハロゲン原子、C1~6アルキル基、C1~6アルコキシ基又はC6~18アリール基を、Rbは、ハロゲン原子、C1~6アルキル基、C1~6アルコキシ基又はC6~18アリール基を表す。)で表される置換基を有するフェニル基を表す。]で表される光学活性2座ホスフィン配位子を表す。R1R2C(NH2)-R3R4C(NH2)は、光学活性ジアミン配位子を表す。R1~R4はそれぞれ独立して、水素原子、無置換若しくは置換基を有するC1~20アルキル基、無置換若しくは置換基を有するC2~20アルケニル基、無置換若しくは置換基を有するC3~8シクロアルキル基、無置換若しくは置換基を有するC4~8シクロアルケニル基、無置換若しくは置換基を有するC6~18アリール基又は無置換若しくは置換基を有するC7~18アラルキル基を表し、R1とR2のいずれかがR3とR4のいずれかと結合して環を形成してもよい。〕で表されるルテニウム化合物。 - 式(I-A)で表されるルテニウム化合物において、式(II-A)で表される光学活性2座ホスフィン配位子が、2,2’-ビス[ビス(3,5-ジメチルフェニル)ホスファニル]-6,6’-ジメチル-1,1’-ビフェニルであることを特徴とする請求項7に記載のルテニウム化合物。
- 式(I-A)で表されるルテニウム化合物において、光学活性ジアミン配位子が、1,1-ビス(4-メトキシフェニル)-2-イソプロピル-1,2-エタンジアミン、1,2-ジフェニル-1,2-エタンジアミン、又は1,2-ジアミノシクロヘキサンであることを特徴とする請求項7又は8に記載のルテニウム化合物。
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CN115160162A (zh) * | 2022-07-11 | 2022-10-11 | 南方科技大学 | 一种α氨基β酮酸酯的不对称氢化方法 |
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CN105085372B (zh) * | 2014-05-12 | 2018-11-16 | 上海交通大学 | 手性γ-氨基醇类化合物的制备方法 |
US20180369083A1 (en) | 2015-12-17 | 2018-12-27 | L'oreal | Water-in-oil emulsion with moisturizing effect containing hydrophobic coated pigments and an aqueous phase at high content |
WO2020096976A1 (en) * | 2018-11-08 | 2020-05-14 | Entegris, Inc. | Chemical vapor deposition processes using ruthenium precursor and reducing gas |
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JP2013043888A (ja) * | 2011-08-22 | 2013-03-04 | Nippon Chem Ind Co Ltd | ケトン類化合物を不斉水素添加する方法 |
CN115160162A (zh) * | 2022-07-11 | 2022-10-11 | 南方科技大学 | 一种α氨基β酮酸酯的不对称氢化方法 |
CN115160162B (zh) * | 2022-07-11 | 2023-11-28 | 南方科技大学 | 一种α氨基β酮酸酯的不对称氢化方法 |
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EP2264000A1 (en) | 2010-12-22 |
EP2264000B1 (en) | 2016-05-11 |
EP2264000A4 (en) | 2011-11-23 |
JPWO2009125565A1 (ja) | 2011-07-28 |
CN101983186B (zh) | 2013-12-11 |
JP5276093B2 (ja) | 2013-08-28 |
US8207379B2 (en) | 2012-06-26 |
CN101983186A (zh) | 2011-03-02 |
KR101243408B1 (ko) | 2013-03-13 |
US20110028749A1 (en) | 2011-02-03 |
KR20100127810A (ko) | 2010-12-06 |
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