JP2008184398A - キラルなイリジウムアクア錯体およびそれを用いた光学活性ヒドロキシ化合物の製造方法 - Google Patents
キラルなイリジウムアクア錯体およびそれを用いた光学活性ヒドロキシ化合物の製造方法 Download PDFInfo
- Publication number
- JP2008184398A JP2008184398A JP2007017670A JP2007017670A JP2008184398A JP 2008184398 A JP2008184398 A JP 2008184398A JP 2007017670 A JP2007017670 A JP 2007017670A JP 2007017670 A JP2007017670 A JP 2007017670A JP 2008184398 A JP2008184398 A JP 2008184398A
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- Prior art keywords
- complex
- formula
- substituent
- represented
- chiral iridium
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- Granted
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- 229910052741 iridium Inorganic materials 0.000 title claims abstract description 70
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 150000002440 hydroxy compounds Chemical class 0.000 title claims description 21
- 238000004519 manufacturing process Methods 0.000 title claims description 20
- 125000001424 substituent group Chemical group 0.000 claims abstract description 72
- 238000009901 transfer hydrogenation reaction Methods 0.000 claims abstract description 33
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 23
- 125000003118 aryl group Chemical group 0.000 claims abstract description 21
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 32
- 125000004432 carbon atom Chemical group C* 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 150000004985 diamines Chemical class 0.000 claims description 17
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 16
- 235000019253 formic acid Nutrition 0.000 claims description 16
- 150000001728 carbonyl compounds Chemical class 0.000 claims description 14
- 239000012046 mixed solvent Substances 0.000 claims description 13
- 150000003839 salts Chemical class 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 7
- 125000001072 heteroaryl group Chemical group 0.000 claims description 7
- 125000005346 substituted cycloalkyl group Chemical group 0.000 claims description 5
- 125000003107 substituted aryl group Chemical group 0.000 claims description 4
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 claims description 3
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 3
- 125000002947 alkylene group Chemical group 0.000 abstract description 5
- -1 N-substituted sulfonyl-ethylenediamine Chemical class 0.000 description 28
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 27
- 238000006243 chemical reaction Methods 0.000 description 22
- 239000002904 solvent Substances 0.000 description 18
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 16
- 150000001875 compounds Chemical class 0.000 description 14
- 239000000243 solution Substances 0.000 description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- OKKJLVBELUTLKV-VMNATFBRSA-N methanol-d1 Chemical compound [2H]OC OKKJLVBELUTLKV-VMNATFBRSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 125000003545 alkoxy group Chemical group 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 6
- 239000003125 aqueous solvent Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 150000001721 carbon Chemical group 0.000 description 5
- SSJXIUAHEKJCMH-UHFFFAOYSA-N cyclohexane-1,2-diamine Chemical compound NC1CCCCC1N SSJXIUAHEKJCMH-UHFFFAOYSA-N 0.000 description 5
- 125000005843 halogen group Chemical group 0.000 description 5
- 150000002503 iridium Chemical class 0.000 description 5
- 125000001624 naphthyl group Chemical group 0.000 description 5
- 238000010898 silica gel chromatography Methods 0.000 description 5
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 4
- ZJRCIQAMTAINCB-UHFFFAOYSA-N benzoylacetonitrile Chemical compound N#CCC(=O)C1=CC=CC=C1 ZJRCIQAMTAINCB-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 230000008034 disappearance Effects 0.000 description 4
- 238000000816 matrix-assisted laser desorption--ionisation Methods 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 239000012044 organic layer Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- 102100028735 Dachshund homolog 1 Human genes 0.000 description 3
- 101000915055 Homo sapiens Dachshund homolog 1 Proteins 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 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
- 125000001188 haloalkyl group Chemical group 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 3
- 125000002524 organometallic group Chemical group 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 125000001544 thienyl group Chemical group 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 2
- JFSJOQODVWQCGJ-UHFFFAOYSA-N 2-(2-methylphenyl)-2-oxoacetic acid Chemical compound CC1=CC=CC=C1C(=O)C(O)=O JFSJOQODVWQCGJ-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910020366 ClO 4 Inorganic materials 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 125000004438 haloalkoxy group Chemical group 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical group 0.000 description 2
- 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 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 2
- PONXTPCRRASWKW-ZIAGYGMSSA-N (1r,2r)-1,2-diphenylethane-1,2-diamine Chemical compound C1([C@@H](N)[C@H](N)C=2C=CC=CC=2)=CC=CC=C1 PONXTPCRRASWKW-ZIAGYGMSSA-N 0.000 description 1
- SBGOGHODWUZHIY-HZPDHXFCSA-N (1r,2r)-n,n'-dimethyl-1,2-bis[3-(trifluoromethyl)phenyl]ethane-1,2-diamine Chemical compound C1([C@@H](NC)[C@H](NC)C=2C=C(C=CC=2)C(F)(F)F)=CC=CC(C(F)(F)F)=C1 SBGOGHODWUZHIY-HZPDHXFCSA-N 0.000 description 1
- SSJXIUAHEKJCMH-WDSKDSINSA-N (1s,2s)-cyclohexane-1,2-diamine Chemical compound N[C@H]1CCCC[C@@H]1N SSJXIUAHEKJCMH-WDSKDSINSA-N 0.000 description 1
- LVHVBUDHMBQPMI-MRVPVSSYSA-N (2r)-2-hydroxy-2-(2-methylphenyl)acetic acid Chemical compound CC1=CC=CC=C1[C@@H](O)C(O)=O LVHVBUDHMBQPMI-MRVPVSSYSA-N 0.000 description 1
- HILDHWAXSORHRZ-VIFPVBQESA-N (3s)-3-hydroxy-3-phenylpropanenitrile Chemical compound N#CC[C@H](O)C1=CC=CC=C1 HILDHWAXSORHRZ-VIFPVBQESA-N 0.000 description 1
- DYLIWHYUXAJDOJ-OWOJBTEDSA-N (e)-4-(6-aminopurin-9-yl)but-2-en-1-ol Chemical compound NC1=NC=NC2=C1N=CN2C\C=C\CO DYLIWHYUXAJDOJ-OWOJBTEDSA-N 0.000 description 1
- HNEGJTWNOOWEMH-UHFFFAOYSA-N 1-fluoropropane Chemical group [CH2]CCF HNEGJTWNOOWEMH-UHFFFAOYSA-N 0.000 description 1
- 125000004343 1-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])(*)C([H])([H])[H] 0.000 description 1
- MEKOFIRRDATTAG-UHFFFAOYSA-N 2,2,5,8-tetramethyl-3,4-dihydrochromen-6-ol Chemical compound C1CC(C)(C)OC2=C1C(C)=C(O)C=C2C MEKOFIRRDATTAG-UHFFFAOYSA-N 0.000 description 1
- 125000004778 2,2-difluoroethyl group Chemical group [H]C([H])(*)C([H])(F)F 0.000 description 1
- 125000003163 2-(2-naphthyl)ethyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(C([H])=C([H])C2=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004777 2-fluoroethyl group Chemical group [H]C([H])(F)C([H])([H])* 0.000 description 1
- 125000003890 2-phenylbutyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000006201 3-phenylpropyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- 239000012327 Ruthenium complex Substances 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- ZVQOOHYFBIDMTQ-UHFFFAOYSA-N [methyl(oxido){1-[6-(trifluoromethyl)pyridin-3-yl]ethyl}-lambda(6)-sulfanylidene]cyanamide Chemical group N#CN=S(C)(=O)C(C)C1=CC=C(C(F)(F)F)N=C1 ZVQOOHYFBIDMTQ-UHFFFAOYSA-N 0.000 description 1
- 125000004054 acenaphthylenyl group Chemical group C1(=CC2=CC=CC3=CC=CC1=C23)* 0.000 description 1
- 150000008062 acetophenones Chemical class 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000000499 benzofuranyl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 description 1
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 125000000259 cinnolinyl group Chemical group N1=NC(=CC2=CC=CC=C12)* 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 125000002704 decyl 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])* 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 125000001028 difluoromethyl group Chemical group [H]C(F)(F)* 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000004785 fluoromethoxy group Chemical group [H]C([H])(F)O* 0.000 description 1
- 125000004216 fluoromethyl group Chemical group [H]C([H])(F)* 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003707 hexyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 239000000852 hydrogen donor Substances 0.000 description 1
- 125000001041 indolyl group Chemical group 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000005956 isoquinolyl group Chemical group 0.000 description 1
- UOPFIWYXBIHPIP-UHFFFAOYSA-N n-(2-amino-1,2-diphenylethyl)-4-methylbenzenesulfonamide Chemical compound C1=CC(C)=CC=C1S(=O)(=O)NC(C=1C=CC=CC=1)C(N)C1=CC=CC=C1 UOPFIWYXBIHPIP-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 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
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- UUEVFMOUBSLVJW-UHFFFAOYSA-N oxo-[[1-[2-[2-[2-[4-(oxoazaniumylmethylidene)pyridin-1-yl]ethoxy]ethoxy]ethyl]pyridin-4-ylidene]methyl]azanium;dibromide Chemical compound [Br-].[Br-].C1=CC(=C[NH+]=O)C=CN1CCOCCOCCN1C=CC(=C[NH+]=O)C=C1 UUEVFMOUBSLVJW-UHFFFAOYSA-N 0.000 description 1
- 125000004115 pentoxy group Chemical group [*]OC([H])([H])C([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 125000004592 phthalazinyl group Chemical group C1(=NN=CC2=CC=CC=C12)* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 125000002294 quinazolinyl group Chemical group N1=C(N=CC2=CC=CC=C12)* 0.000 description 1
- 125000005493 quinolyl group Chemical group 0.000 description 1
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F17/00—Metallocenes
- C07F17/02—Metallocenes of metals of Groups 8, 9 or 10 of the Periodic System
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B53/00—Asymmetric syntheses
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
- C07C205/13—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by hydroxy groups
- C07C205/14—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by hydroxy groups having nitro groups and hydroxy groups bound to acyclic carbon atoms
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Abstract
Description
[1]式(1):
で表されるキラルなイリジウムアクア錯体(以下、キラルなイリジウムアクア錯体(1)ともいう)。
[4]キラルなイリジウムアクア錯体が、式(2−S):
[6]キラルなイリジウムアクア錯体が、式(3−R):
[8]キラルなイリジウムアクア錯体が式(4−R):
[10]キラルなイリジウムアクア錯体が式(5−R):
[12]不斉移動水素化反応が、蟻酸またはその塩の存在下で行われる、上記[11]に記載の製造方法。
[13]不斉移動水素化反応が、蟻酸存在下で行われる、上記[11]に記載の製造方法。
[14]不斉移動水素化反応が、水または水−アルコール混合溶媒中で行われる、上記[11]に記載の製造方法。
加えて、本発明のキラルなイリジウムアクア錯体(1)は、空気や水に対する安定性が良好である。また本発明のキラルなイリジウムアクア錯体(1)を用いて不斉移動水素化反応を行うと、従来のイリジウム錯体と比較して、より高い収率や立体選択性を達成することができる。
R1またはR2で示される「置換基を有していてもよいアリール基」における「アリール基」としては、炭素数6〜14のアリール基が好ましく、フェニル、ナフチル、アントリル、フェナントリル、アセナフチレニル、ビフェニリル等が挙げられ、中でも、フェニルが好ましい。「置換基を有していてもよいアリール基」における「置換基」としては、ハロゲン原子、炭素数1〜6のアルキル基、炭素数1〜6のハロアルキル基、炭素数1〜6のアルコキシ基、炭素数1〜6のハロアルコキシ基、ニトロ基、カルボキシル基、シアノ基等が挙げられる。
炭素数1〜6のアルキル基は、直鎖状でも分岐状でもよく、例えば、メチル、エチル、プロピル、イソプロピル、ブチル、イソブチル、sec−ブチル、tert−ブチル、ペンチル、イソペンチル、ネオペンチル、ヘキシル等が挙げられる。
炭素数1〜6のハロアルキル基は、直鎖状でも分岐状でもよく、例えば、フルオロメチル、ジフルオロメチル、トリフルオロメチル、2−フルオロエチル、2,2−ジフルオロエチル、2,2,2−トリフルオロエチル、3−フルオロプロピル、4−フルオロブチル、5−フルオロペンチル、6−フルオロヘキシル等が挙げられる。
炭素数1〜6のアルコキシ基は、直鎖状でも分岐状でもよく、例えば、メトキシ、エトキシ、プロポキシ、イソプロポキシ、ブトキシ、イソブトキシ、sec−ブトキシ、tert−ブトキシ、ペンチルオキシ、イソペンチルオキシ、ネオペンチルオキシ、ヘキシルオキシ等が挙げられる。
炭素数1〜6のハロアルコキシ基は、直鎖状でも分岐状でもよく、例えば、フルオロメトキシ、ジフルオロメトキシ、トリフルオロメトキシ、2−フルオロエトキシ、2,2−ジフルオロエトキシ、2,2,2−トリフルオロエトキシ、3−フルオロプロポキシ、4−フルオロブトキシ、5−フルオロペンチルオキシ、6−フルオロヘキシルオキシ等が挙げられる。
ここで、キラルなジアミン(9)の好適な具体例としては、
上記のキラルなジアミン(9)は、ラセミ体(トランス体の1:1混合物)でなく、その鏡像体過剰率は0%eeより大きいが、100%eeまで任意の値であり、90%ee以上、特に95%ee以上であることが好ましい。
溶媒としては、水、メタノール等のアルコール、およびこれらの混合物等が挙げられ、中でも、水または水−アルコールの混合溶媒が好ましい。混合溶媒の場合、水とアルコールの含有比(容量比)は、キラルなジアミンの種類にもよるが、通常1:1〜10:1であり、好ましくは1:1〜5:1である。溶媒の使用量は、イリジウム錯体(8)1gに対して、通常3〜100mlモルであり、操作性と経済性の両立の観点から、好ましくは10〜65mlである。
反応終了後、反応混合物を濃縮することにより、キラルなイリジウムアクア錯体(1)が得られる。なお、必要に応じて、再結晶等の操作により精製してもよい。
当該反応は、通常溶媒中、水素供与性化合物の存在下で行われ、キラルなイリジウムアクア錯体(1)の溶液にカルボニル化合物(6)を添加して攪拌することにより行われる。
水素供与性化合物としては、例えば、蟻酸またはその塩が好ましく、転換率が良好である観点から、蟻酸が特に好ましい。水素供与性化合物の使用量は、カルボニル化合物(6)1モルに対して、通常1〜100モルであり、経済性の観点から、好ましくは2〜10モルである。
なお、水素供与性化合物として蟻酸を使用する場合、この蟻酸は溶媒を兼ねていてもよい。
溶媒としては、水、メタノール等のアルコール、およびそれらの混合物等が挙げられ、中でも、水または水−アルコールの混合溶媒が好ましい。混合溶媒の場合、水とアルコールの含有比(容量比)は、原料のカルボニル化合物(6)および錯体の種類や量にもよるが、通常10:1〜1:10であり、好ましくは3:1〜1:3である。溶媒の使用量は、カルボニル化合物(6)1gに対して、通常1〜100mlであり、操作性と経済性の観点から、好ましくは3〜50mlである。
Organometallics 1999, 18, 5470に記載の方法に従って、水(12ml)中Ag2SO4(3.36mmol,1.05g)および[Cp*IrCl2]2(1.68mmol,1.34g)の混合物を室温で12時間攪拌し、次いで、濾過してAgClを除去した。溶媒を減圧留去して、黄色固体の目的物(1.55g,97%)を得た。
1H NMR (300 MHz, D2O) δ: 1.59 (s, 15 H).
Organometallics 2001, 20, 4903に記載の方法に従って、[Cp*Ir(H2O)3](SO4)(0.21mmol,100mg)およびビピリジン(0.22mmol,34mg)の水(1.5ml)溶液を室温で12時間攪拌した。溶媒を減圧留去して、黄色固体の目的物(定量的)を得た。
1H NMR (300 MHz, D2O) δ: 1.65 (s, 15 H), 7.87 (t, J = 5.7 Hz, 2 H), 8.32 (t, J = 8.1 Hz, 2 H), 8.51 (d, J = 8.1 Hz, 2 H), 9.10 (d, J = 5.7 Hz, 2 H).
1H NMR (300 MHz, MeOD) δ: 1.15-1.46 (m, 4H), 1.59-1.71 (m, 2H), 1.74 (s, 15H), 2.01-2.19 (m, 3H), 2.50-2.60 (m, 1H), 4.65-4.75 (m, 1H), 5.20-5.40 (m, 1H), 5.42-5.75 (m, 2H).
13C NMR (75 MHz, MeOD) δ: 8.8, 25.6, 25.7, 33.7, 34.5, 58.7, 63.7, 86.1.
HR-MALDI calcd for C16H28IrN2[M-SO4-H2O-H]+, 441.1882. Found 441.1876.
[α]D 30 -44.24 (c 0.25, EtOH).
1H NMR (300 MHz, D2O) δ: 1.75 (s, 15H), 4.18 (br s, 2H), 7.20-7.28 (m, 10H).
1H NMR (300 MHz, MeOD) δ: 1.81 (s, 15H), 3.90-4.00 (m, 1H), 4.28-4.38 (m, 1H), 7.14-7.41 (m, 10H).
13C NMR (75 MHz, MeOD) δ: 8.9, 63.7, 68.3, 86.5, 128.7, 129.0, 129.1, 129.3, 137.9, 138.9.
HR-MALDI calcd for C24H30IrN2[M-SO4-H2O-H]+, 539.2038. Found 539.1827.
[α]D 30 +70.43 (c 0.45, CHCl3).
1H NMR (300 MHz, MeOD) δ: 1.75 (s, 15H), 2.68 (s, 3H), 2.91 (s, 3H), 3.85 (d, J = 12.3 Hz, 1H), 4.08 (d, J = 12.3 Hz, 1H), 7.15-7.29 (m, 10H).
13C NMR (75 MHz, MeOD) δ: 8.9, 37.1, 41.5, 72.6, 76.8, 87.7, 129.3, 129.5, 129.9, 135.0, 136.1.
HR-MALDI calcd for C26H34IrN2[M-SO4-H2O-H]+ 567.2347, found 567.2338.
[α]D 24 +75.48 (c 0.43, EtOH).
1H NMR (300 MHz, MeOD) δ: 1.74 (s, 15H), 2.70 (s, 3H), 2.94 (s, 3H), 4.05 (d, J = 11.9 Hz, 1H), 4.27 (d, J = 11.9 Hz, 1H), 7.45-7.80 (m, 8H).
13C NMR (75 MHz, MeOD) δ: 9.1, 37.4, 41.8, 71.9, 75.8, 87.9, 123.7 (c, J = 279.9 Hz), 123.7 (c, J = 270.0 Hz), 126.2 (c, J = 3.7 Hz), 126.5 (c, J = 3.6 Hz), 130.1, 130.8, 131.8, 131.3 (c, J = 32 Hz), 135.9, 137.3.
HR-MALDI calcd for C28H32F6IrN2[M-SO4-H2O-H]+ 703.2099, found 703.2103.
[α]D 27 +57.45 (c 0.50, EtOH).
水−メタノールの1:1混合溶媒(容量比、5ml)のイリジウムアクア錯体(表1の[Cp*Ir(ligand)H2O](SO4),2−シアノアセトフェノンに対して0.5mol%)溶液に、2−シアノアセトフェノン(1mmol)および蟻酸またはその塩(表1のHCO2X,5mmol)を室温で加え、混合物を70℃で攪拌した。TLCにて2−シアノアセトフェノンの消失を確認した後、NaCl水溶液(20ml)で反応を停止した。酢酸エチル(20ml×3)で抽出し、合わせた有機層を無水Na2SO4で乾燥し、濃縮した。残渣をシリカゲルカラムクロマトグラフィー(展開溶媒:ジクロロメタン:メタノール=20:1)で精製して、(S)−3−フェニル−3−ヒドロキシプロピオニトリルを得た。変換率、eeを表1に示す。
{Cp*Ir[(R,R)−Me−CF3−DPEN](H2O)}(SO4)を用いて以下の反応を行った。
{Cp*Ir[(R,R)−Me−CF3−DPEN](H2O)}(SO4)を用いて以下の反応を行った。
水−蟻酸の1:1混合溶媒(容量比、5ml)の{Cp*Ir[(R,R)−Me−CF3−DPEN](H2O)}(SO4)(2−メチルフェニルグリオキシル酸に対して0.5mol%)溶液に、2−メチルフェニルグリオキシル酸(1mmol)を室温で加え、混合物を室温で攪拌した。TLCにて2−メチルフェニルグリオキシル酸の消失を確認した後、NaCl水溶液(20ml)で反応を停止した。酢酸エチル(20ml×3)で抽出し、合わせた有機層を無水Na2SO4で乾燥し、濃縮した。残渣をシリカゲルカラムクロマトグラフィー(展開溶媒:ジクロロメタン:メタノール=20:1)で精製して、対応する(R)−2−メチルフェニル−2−ヒドロキシ酢酸を得た。収率95%、ee83%。
加えて、本発明のキラルなイリジウムアクア錯体(1)は、空気や水に対する安定性が良好である。また本発明のキラルなイリジウムアクア錯体(1)を用いて不斉移動水素化反応を行うと、従来のイリジウム錯体と比較して、より高い収率や立体選択性を達成することができる。
Claims (14)
- 不斉移動水素化反応が、蟻酸またはその塩の存在下で行われる、請求項11に記載の製造方法。
- 不斉移動水素化反応が、蟻酸存在下で行われる、請求項11に記載の製造方法。
- 不斉移動水素化反応が、水または水−アルコール混合溶媒中で行われる、請求項11に記載の製造方法。
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EP08710614.2A EP2123661B1 (en) | 2007-01-29 | 2008-01-29 | Chiral iridium aqua complex and method for producing optically active hydroxy compound by using the same |
CN200880003302A CN101652376A (zh) | 2007-01-29 | 2008-01-29 | 手性铱水络合物和使用它的旋光性羟基化合物的制备方法 |
KR1020097016677A KR20090118032A (ko) | 2007-01-29 | 2008-01-29 | 키랄 이리듐 아쿠아 착물 및 이를 사용한 광학 활성 히드록시 화합물의 제조 방법 |
US12/524,632 US8044224B2 (en) | 2007-01-29 | 2008-01-29 | Chiral iridium aqua complex and method for producing optically active hydroxy compound by using the same |
PCT/JP2008/051287 WO2008093668A1 (ja) | 2007-01-29 | 2008-01-29 | キラルなイリジウムアクア錯体およびそれを用いた光学活性ヒドロキシ化合物の製造方法 |
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AU2012240314A1 (en) * | 2011-04-04 | 2013-05-02 | Gilead Sciences, Inc. | Process for the preparation of an HIV integrase inhibitor |
US9073827B2 (en) | 2011-04-28 | 2015-07-07 | Takasago International Corporation | Method for producing diamine compound |
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JP5006059B2 (ja) | 2012-08-22 |
EP2123661A1 (en) | 2009-11-25 |
CN101652376A (zh) | 2010-02-17 |
KR20090118032A (ko) | 2009-11-17 |
WO2008093668A1 (ja) | 2008-08-07 |
US20100016618A1 (en) | 2010-01-21 |
EP2123661B1 (en) | 2013-05-22 |
US8044224B2 (en) | 2011-10-25 |
EP2123661A4 (en) | 2011-08-17 |
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