JP2006521385A - アキラルジオールによって橋架けされた光学活性ビスホスファイトから製造された非対称触媒 - Google Patents
アキラルジオールによって橋架けされた光学活性ビスホスファイトから製造された非対称触媒 Download PDFInfo
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- JP2006521385A JP2006521385A JP2006508980A JP2006508980A JP2006521385A JP 2006521385 A JP2006521385 A JP 2006521385A JP 2006508980 A JP2006508980 A JP 2006508980A JP 2006508980 A JP2006508980 A JP 2006508980A JP 2006521385 A JP2006521385 A JP 2006521385A
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- 150000002009 diols Chemical class 0.000 title description 5
- 239000011982 enantioselective catalyst Substances 0.000 title 1
- 239000003446 ligand Substances 0.000 claims abstract description 138
- 238000000034 method Methods 0.000 claims abstract description 119
- 239000003054 catalyst Substances 0.000 claims abstract description 75
- 230000008569 process Effects 0.000 claims abstract description 71
- 238000007037 hydroformylation reaction Methods 0.000 claims abstract description 53
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims abstract 3
- 238000006243 chemical reaction Methods 0.000 claims description 54
- 239000010948 rhodium Substances 0.000 claims description 54
- 229910052751 metal Inorganic materials 0.000 claims description 48
- 239000002184 metal Substances 0.000 claims description 48
- 150000001336 alkenes Chemical class 0.000 claims description 36
- 125000001424 substituent group Chemical group 0.000 claims description 33
- -1 VIB metals Chemical class 0.000 claims description 31
- 229910052703 rhodium Inorganic materials 0.000 claims description 28
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 27
- 229910052739 hydrogen Inorganic materials 0.000 claims description 22
- 239000001257 hydrogen Substances 0.000 claims description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 21
- SJNALLRHIVGIBI-UHFFFAOYSA-N allyl cyanide Chemical compound C=CCC#N SJNALLRHIVGIBI-UHFFFAOYSA-N 0.000 claims description 18
- 239000002243 precursor Substances 0.000 claims description 18
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 17
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 17
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 17
- 125000003118 aryl group Chemical group 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- IMHDGJOMLMDPJN-UHFFFAOYSA-N biphenyl-2,2'-diol Chemical group OC1=CC=CC=C1C1=CC=CC=C1O IMHDGJOMLMDPJN-UHFFFAOYSA-N 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- 239000001301 oxygen Substances 0.000 claims description 13
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 13
- 150000005347 biaryls Chemical group 0.000 claims description 10
- 150000002739 metals Chemical class 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 230000003287 optical effect Effects 0.000 claims description 10
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 9
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 8
- 239000012018 catalyst precursor Substances 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 150000002430 hydrocarbons Chemical group 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 6
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 229910052707 ruthenium Inorganic materials 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- NKKMVIVFRUYPLQ-NSCUHMNNSA-N crotononitrile Chemical compound C\C=C\C#N NKKMVIVFRUYPLQ-NSCUHMNNSA-N 0.000 claims description 4
- 230000006698 induction Effects 0.000 claims description 4
- 229910052741 iridium Inorganic materials 0.000 claims description 4
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052762 osmium Inorganic materials 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 3
- 238000006482 condensation reaction Methods 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 3
- 230000009467 reduction Effects 0.000 claims description 3
- 238000006722 reduction reaction Methods 0.000 claims description 3
- YODZBWQNWOMCRD-UHFFFAOYSA-N 1-(1-phenylethenoxy)-4-(trifluoromethyl)benzene Chemical compound C1=CC(C(F)(F)F)=CC=C1OC(=C)C1=CC=CC=C1 YODZBWQNWOMCRD-UHFFFAOYSA-N 0.000 claims description 2
- VTMSSJKVUVVWNJ-UHFFFAOYSA-N 1-ethenyl-4-(2-methylpropyl)benzene Chemical compound CC(C)CC1=CC=C(C=C)C=C1 VTMSSJKVUVVWNJ-UHFFFAOYSA-N 0.000 claims description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 2
- 238000005576 amination reaction Methods 0.000 claims description 2
- NHOGGUYTANYCGQ-UHFFFAOYSA-N ethenoxybenzene Chemical compound C=COC1=CC=CC=C1 NHOGGUYTANYCGQ-UHFFFAOYSA-N 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims 3
- 125000004665 trialkylsilyl group Chemical group 0.000 claims 2
- JKJCKJFOSSLMJF-UHFFFAOYSA-N (5-ethenylthiophen-2-yl)-phenylmethanone Chemical compound S1C(C=C)=CC=C1C(=O)C1=CC=CC=C1 JKJCKJFOSSLMJF-UHFFFAOYSA-N 0.000 claims 1
- GJYSYQQXHBPJRD-UHFFFAOYSA-N 1-(2-methylpropyl)-4-prop-1-enylbenzene Chemical compound CC=CC1=CC=C(CC(C)C)C=C1 GJYSYQQXHBPJRD-UHFFFAOYSA-N 0.000 claims 1
- YYMLNVWFCKTXSJ-UHFFFAOYSA-N 1-ethenyl-3-[2-[2-(3-ethenylphenyl)phenoxy]phenyl]benzene Chemical compound C=CC1=CC=CC(C=2C(=CC=CC=2)OC=2C(=CC=CC=2)C=2C=C(C=C)C=CC=2)=C1 YYMLNVWFCKTXSJ-UHFFFAOYSA-N 0.000 claims 1
- GKVVFBRUOAPKMI-UHFFFAOYSA-N 2-(4-ethenylphenyl)-3h-isoindol-1-one Chemical compound C1=CC(C=C)=CC=C1N1C(=O)C2=CC=CC=C2C1 GKVVFBRUOAPKMI-UHFFFAOYSA-N 0.000 claims 1
- NTYHSGAJVIGSEY-UHFFFAOYSA-N 4-ethenyl-2-fluoro-1-phenylbenzene Chemical group FC1=CC(C=C)=CC=C1C1=CC=CC=C1 NTYHSGAJVIGSEY-UHFFFAOYSA-N 0.000 claims 1
- QROGIFZRVHSFLM-QHHAFSJGSA-N [(e)-prop-1-enyl]benzene Chemical compound C\C=C\C1=CC=CC=C1 QROGIFZRVHSFLM-QHHAFSJGSA-N 0.000 claims 1
- 238000005917 acylation reaction Methods 0.000 claims 1
- 230000029936 alkylation Effects 0.000 claims 1
- 238000005804 alkylation reaction Methods 0.000 claims 1
- HPOIBYCOUNOMCS-UHFFFAOYSA-N bis[2-(3-ethenylphenyl)phenyl]methanone Chemical compound C(=C)C=1C=C(C=CC=1)C1=C(C=CC=C1)C(=O)C1=C(C=CC=C1)C1=CC(=CC=C1)C=C HPOIBYCOUNOMCS-UHFFFAOYSA-N 0.000 claims 1
- UHGBNCQLFKYEJE-UHFFFAOYSA-N bis[3-(4-ethenylphenyl)thiophen-2-yl]methanone Chemical compound C1=CC(C=C)=CC=C1C1=C(C(=O)C2=C(C=CS2)C=2C=CC(C=C)=CC=2)SC=C1 UHGBNCQLFKYEJE-UHFFFAOYSA-N 0.000 claims 1
- 230000005494 condensation Effects 0.000 claims 1
- 230000032050 esterification Effects 0.000 claims 1
- 238000005886 esterification reaction Methods 0.000 claims 1
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 132
- 239000000047 product Substances 0.000 description 48
- 239000007787 solid Substances 0.000 description 27
- 238000005481 NMR spectroscopy Methods 0.000 description 24
- 150000001299 aldehydes Chemical class 0.000 description 21
- 238000012512 characterization method Methods 0.000 description 21
- 239000000706 filtrate Substances 0.000 description 21
- 238000002360 preparation method Methods 0.000 description 19
- 229910052698 phosphorus Inorganic materials 0.000 description 17
- 239000011574 phosphorus Substances 0.000 description 17
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 16
- 239000007858 starting material Substances 0.000 description 16
- 239000002904 solvent Substances 0.000 description 15
- 238000004519 manufacturing process Methods 0.000 description 13
- 239000012429 reaction media Substances 0.000 description 13
- 238000004458 analytical method Methods 0.000 description 12
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 11
- 229910052727 yttrium Inorganic materials 0.000 description 11
- 125000004432 carbon atom Chemical group C* 0.000 description 10
- 239000000758 substrate Substances 0.000 description 10
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- 125000001183 hydrocarbyl group Chemical group 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 238000011914 asymmetric synthesis Methods 0.000 description 8
- 238000011065 in-situ storage Methods 0.000 description 8
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
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- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 125000003545 alkoxy group Chemical group 0.000 description 6
- 125000003710 aryl alkyl group Chemical group 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- HBAQYPYDRFILMT-UHFFFAOYSA-N 8-[3-(1-cyclopropylpyrazol-4-yl)-1H-pyrazolo[4,3-d]pyrimidin-5-yl]-3-methyl-3,8-diazabicyclo[3.2.1]octan-2-one Chemical class C1(CC1)N1N=CC(=C1)C1=NNC2=C1N=C(N=C2)N1C2C(N(CC1CC2)C)=O HBAQYPYDRFILMT-UHFFFAOYSA-N 0.000 description 5
- HRJABHWZEQHPFS-UHFFFAOYSA-N [1-[2-(12,14-dioxa-13-phosphapentacyclo[13.8.0.02,11.03,8.018,23]tricosa-1(15),2(11),3,5,7,9,16,18,20,22-decaen-13-yloxy)naphthalen-1-yl]naphthalen-2-yl]-diphenylphosphane Chemical compound O1C=2C=CC3=CC=CC=C3C=2C(C2=CC=CC=C2C=C2)=C2OP1OC1=CC=C2C=CC=CC2=C1C(C1=CC=CC=C1C=C1)=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 HRJABHWZEQHPFS-UHFFFAOYSA-N 0.000 description 5
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 5
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- GGRQQHADVSXBQN-FGSKAQBVSA-N carbon monoxide;(z)-4-hydroxypent-3-en-2-one;rhodium Chemical compound [Rh].[O+]#[C-].[O+]#[C-].C\C(O)=C\C(C)=O GGRQQHADVSXBQN-FGSKAQBVSA-N 0.000 description 5
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- FXPPNKAYSGWCQG-UHFFFAOYSA-N 2-acetoxypropanal Chemical compound O=CC(C)OC(C)=O FXPPNKAYSGWCQG-UHFFFAOYSA-N 0.000 description 3
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- 125000004423 acyloxy group Chemical group 0.000 description 3
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- 125000000440 benzylamino group Chemical group [H]N(*)C([H])([H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 3
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- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 3
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- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 2
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- HVAMZGADVCBITI-UHFFFAOYSA-M pent-4-enoate Chemical compound [O-]C(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-M 0.000 description 1
- GTCCGKPBSJZVRZ-UHFFFAOYSA-N pentane-2,4-diol Chemical compound CC(O)CC(C)O GTCCGKPBSJZVRZ-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000000825 pharmaceutical preparation Substances 0.000 description 1
- 229940127557 pharmaceutical product Drugs 0.000 description 1
- 125000000286 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
- 125000005499 phosphonyl group Chemical group 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- LFGREXWGYUGZLY-UHFFFAOYSA-N phosphoryl Chemical group [P]=O LFGREXWGYUGZLY-UHFFFAOYSA-N 0.000 description 1
- 150000003057 platinum Chemical class 0.000 description 1
- FHMDYDAXYDRBGZ-UHFFFAOYSA-N platinum tin Chemical compound [Sn].[Pt] FHMDYDAXYDRBGZ-UHFFFAOYSA-N 0.000 description 1
- HRGDZIGMBDGFTC-UHFFFAOYSA-N platinum(2+) Chemical class [Pt+2] HRGDZIGMBDGFTC-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000003389 potentiating effect Effects 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- KJBRZWADVLEUIE-UHFFFAOYSA-N propyl oct-7-enoate Chemical compound CCCOC(=O)CCCCCC=C KJBRZWADVLEUIE-UHFFFAOYSA-N 0.000 description 1
- WHFQAROQMWLMEY-UHFFFAOYSA-N propylene dimer Chemical compound CC=C.CC=C WHFQAROQMWLMEY-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- GTCKPGDAPXUISX-UHFFFAOYSA-N ruthenium(3+);trinitrate Chemical compound [Ru+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GTCKPGDAPXUISX-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 125000004079 stearyl 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])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])[H] 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 229910052717 sulfur Chemical group 0.000 description 1
- 239000011593 sulfur Chemical group 0.000 description 1
- 230000000153 supplemental effect Effects 0.000 description 1
- 230000001225 therapeutic effect Effects 0.000 description 1
- 239000012974 tin catalyst Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 239000003053 toxin Substances 0.000 description 1
- 231100000765 toxin Toxicity 0.000 description 1
- GKASDNZWUGIAMG-UHFFFAOYSA-N triethyl orthoformate Chemical compound CCOC(OCC)OCC GKASDNZWUGIAMG-UHFFFAOYSA-N 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
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Abstract
Description
を有する新規な光学活性配位子に関する。この配位子の置換されたビアリール部分への前駆体、例えば2,2’−ビアリールジオールは、光学的に活性である。
によって表されるものが含まれる。
を有する前記の光学活性配位子に関する。この配位子の置換されたビアリール部分(portion)は光学的に活性である。
〔実施例〕
実施例1:(R)−(ビフェン(BIPHEN))PBrの製造
(R)−ビフェン−H2(ストレム・ケミカル社(Strem Chemical)から得られた、4.06g、11.45ミリモル)を、100mLのトルエン中に溶解させた。トリエチルアミン(3.25mL、23.31ミリモル)を添加した。三臭化リン(1.1mL、11.6ミリモル)を、この反応混合物に添加し、次いで18時間攪拌した。この懸濁液を濾過し、そして濾液を蒸発させて、(R)−(ビフェン)ブロミダイト(bromidite)を、構造:
31P{1H}NMR(C6D6)δ184;1H NMR(C6D6)δ7.18(s,1H),7.08(s,1H),1.93(s,3H),1.92(s,3H),1.57(s,3H),1.56(s,3H),1.48(s,9H),1.39(s,9H)。
15mLのトルエン中の2,2’−ビフェノール(212mg、1.14ミリモル)及び300μLのEt3Nの溶液を、20mLのトルエン中の[(R)−(ビフェン)]PBr(983mg、2.27ミリモル)の溶液に添加した。この溶液を環境温度で18時間攪拌し、次いで濾過した。濾液を蒸発させて白色固体にし、これをMeCNと共にすりつぶした。上澄み液をデカンテーションし、そして固体生成物を真空下で乾燥させた(737mg、収率68%)。31P{1H}NMR(C6D6)δ134;1H NMR(C6D6)δ7.48(dd,2H);7.31(d,2H),7.25(s,2H),7.23(s,2H),7.03(dt,2H),6.86(dt,2H),2.17(s,6H),2.09(s,6H),1.83(s,6H),1.76(s,6H),1.49(s,18H),1.46(s,18H)。NMRキャラクタリゼーションによって、この生成物が、構造:
5mLのトルエン中のエチレングリコール(36.6mg、0.589ミリモル)及び240μLのEt3Nの溶液を、10mLのトルエン中の[(R)−(ビフェン)]PBr(522mg、1.20ミリモル)の溶液に添加した。この溶液を環境温度で18時間攪拌し、次いで濾過した。濾液を蒸発させて無色の油にし、これをMeCNと共にすりつぶした。上澄み液をデカンテーションし、そして油状固体生成物を真空下で乾燥させた(480mg、収率98%)。NMRキャラクタリゼーションによって、この生成物が、構造:
5mLのトルエン中のネオペンチルグリコール(71.0mg、0.68ミリモル)及び260μLのEt3Nの溶液を、10mLのトルエン中の[(R)−(ビフェン)]PBr(583mg、1.34ミリモル)の溶液に添加した。この溶液を環境温度で2時間攪拌し、次いで濾過した。濾液を蒸発させて白色固体にし、これを真空下で乾燥させた(0.59g、収率99%)。NMRキャラクタリゼーションによって、この生成物が、構造:
5mLのトルエン中のN−Me−ジエタノールアミン(77.8mg、0.653ミリモル)及び300μLのEt3Nの溶液を、10mLのトルエン中の[(R)−(ビフェン)]PBr(550mg、1.27ミリモル)の溶液に添加した。この溶液を環境温度で18時間攪拌し、次いで濾過した。濾液を蒸発させて白色固体にし、これを真空下で乾燥させた(425mg、収率74%)。NMRキャラクタリゼーションによって、この生成物が、構造:
5mLのトルエン中の1,2−ベンゼンジメタノール(82.5mg、0.598ミリモル)及び240μLのEt3Nの溶液を、10mLのトルエン中の[(R)−(ビフェン)]PBr(527mg、1.22ミリモル)の溶液に添加した。この溶液を環境温度で2.5時間攪拌し、次いで濾過した。濾液を蒸発させて無色固体にし、これを真空下で乾燥させた(0.543g、収率49%)。NMRキャラクタリゼーションによって、この生成物が、構造:
5mLのトルエン中の2,2’−ビフェニルジメタノール(147.1mg、0.686ミリモル)及び240μLのEt3Nの溶液を、10mLのトルエン中の[(R)−(ビフェン)]PBr(596mg、1.38ミリモル)の溶液に添加した。この溶液を環境温度で3.5時間攪拌し、次いで濾過した。濾液を蒸発させて白色固体にし、これを真空下で乾燥させた(0.670g、収率98%)。NMRキャラクタリゼーションによって、この生成物が、構造:
5mLのトルエン中の1,3−プロパンジオール(46.0mg、0.604ミリモル)及び220μLのEt3Nの溶液を、10mLのトルエン中の[(R)−(ビフェン)]PBr(524mg、1.21ミリモル)の溶液に添加した。この溶液を環境温度で18時間攪拌し、次いで濾過した。濾液を蒸発させて白色固体にし、これを真空下で乾燥させた(0.500g、収率98%)。NMRキャラクタリゼーションによって、この生成物が、構造:
10mLのトルエン中の1,1’−メチレンビナフトール(208.0mg、0.692ミリモル)及び240μLのEt3Nの溶液を、10mLのトルエン中の[(R)−(ビフェン)]PBr(606mg、1.40ミリモル)の溶液に添加した。この溶液を環境温度で18時間攪拌し、次いで濾過した。濾液を蒸発させてピンク色固体にし、これを8mLのMeCNと共にすりつぶして白色固体を得、これを真空下で乾燥させた(0.688g、収率93%)。NMRキャラクタリゼーションによって、この生成物が、構造:
10mLのトルエン中の1,1’−メチレン−5,5’−ジクロロビスフェノール(185mg、0.687ミリモル)及び240μLのEt3Nの溶液を、10mLのトルエン中の[(R)−(ビフェン)]PBr(589mg、1.36ミリモル)の溶液に添加した。この溶液を環境温度で4時間攪拌し、次いで濾過した。濾液を蒸発させて白色固体にし、これをMeCNと共にすりつぶして白色固体を得、これを真空下で乾燥させた(0.533g、収率75%)。NMRキャラクタリゼーションによって、この生成物が、構造:
10mLのトルエン中の2−ヒドロキシベンジルアルコール(70.7mg、0.570ミリモル)及び240μLのEt3Nの溶液を、10mLのトルエン中の[(R)−(ビフェン)]PBr(502mg、1.16ミリモル)の溶液に添加した。この溶液を環境温度で14時間攪拌し、次いで濾過した。濾液を蒸発させて白色フォームにし、これを沸騰するMeCN中に溶解させた。この溶液を−35℃で貯蔵し、そして白色固体を製造し、これを真空下で乾燥させた(0.372g、収率72%)。NMRキャラクタリゼーションによって、この生成物が、構造:
10mLのトルエン中のジフェン酸(145mg、0.600ミリモル)及び240μLのEt3Nの溶液を、10mLのトルエン中の[(R)−(ビフェン)]PBr(522mg、1.20ミリモル)の溶液に添加した。この溶液を環境温度で14時間攪拌し、次いで濾過した。濾液を蒸発させて薄黄色固体にし、これをMeCNと共にすりつぶした。得られた白色固体を真空下で乾燥させた(0.445g、収率74%)。NMRキャラクタリゼーションによって、この生成物が、構造:
10mLのトルエン中のコハク酸(74.7mg、0.632ミリモル)及び240μLのEt3Nの溶液を、10mLのトルエン中の[(R)−(ビフェン)]PBr(546mg、1.26ミリモル)の溶液に添加した。この溶液を環境温度で1時間攪拌し、次いで濾過した。濾液を蒸発させて白色固体にした(0.551g、収率98%)。NMRキャラクタリゼーションによって、この生成物が、構造:
(S)−3,3’−Me3Si−ビノール−H2(非特許文献6により記載された方法に従って製造した;5.90g、14.0ミリモル)を、20mLのトルエン中に溶解させた。トリエチルアミン(3.8mL)を添加した。この溶液を、200mLのトルエン中の三臭化リン(3.78g)の溶液に添加した。得られた懸濁液を1時間攪拌し、次いで濾過した。濾液を蒸発させて、(S)−(3,3’−Me3Si−ビノール)PBrを、構造:
5mLのトルエン中のネオペンチルグリコール(64.2mg、0.616ミリモル)及び260μLのEt3Nの溶液を、10mLのトルエン中の(S)−(3,3’−Me3Si−ビノール)PBr(669mg、1.24ミリモル)の溶液に添加した。この溶液を環境温度で3時間攪拌し、次いで濾過した。濾液を蒸発させて薄黄色泡状固体にし、これを3mLのMeCNと共にすりつぶし、次いで真空下で乾燥させた(0.503g、収率80%)。NMRキャラクタリゼーションによって、この生成物が、構造:
5mLのトルエン中の2,2‘−ビフェノール(107.6mg、0.578ミリモル)及び240μLのEt3Nの溶液を、10mLのトルエン中の(S)−(3,3’−Me3Si−ビノール)PBr(646mg、1.20ミリモル)の溶液に添加した。この溶液を環境温度で3時間攪拌し、次いで濾過した。濾液を蒸発させて薄黄褐色固体にし、これを3mLのMeCNと共にすりつぶした。得られた白色固体を真空下で乾燥させた(0.59g、収率92%)。NMRキャラクタリゼーションによって、この生成物が、構造:
5mLのトルエン中のエチレングリコール(29.4mg、0.473ミリモル)及び160μLのEt3Nの溶液を、10mLのトルエン中の(S)−(3,3’−Me3Si−ビノール)PBr(512mg、0.949ミリモル)の溶液に添加した。この溶液を環境温度で2時間攪拌し、次いで濾過した。濾液を蒸発させて無色の油にした(0.423g、収率91%)。NMRキャラクタリゼーションによって、この生成物が、構造:
10mLのトルエン中の1,3−ベンゼンジメタノール(89.4mg、0.647ミリモル)及び240μLのEt3Nの溶液を、10mLのトルエン中の[(R)−(ビフェン)]PBr(569mg、1.31ミリモル)の溶液に添加した。この溶液を環境温度で18時間攪拌し、次いで濾過した。濾液を蒸発させて白色固体にした(0.576g、収率98%)。NMRキャラクタリゼーションによって、この生成物が、構造:
5mLのトルエン中の1,4−ブタンジオール(33.4mg、0.370ミリモル)及び140μLのEt3Nの溶液を、10mLのトルエン中の(S)−(3,3’−Me3Si−ビノール)PBr(410mg、0.761ミリモル)の溶液に添加した。この溶液を環境温度で3時間攪拌し、次いで濾過した。濾液を蒸発させて油状白色固体にした(0.359g、収率96%)。NMRキャラクタリゼーションによって、この生成物が、構造:
5mLのトルエン中の1,4−ブタンジオール(55mg、0.61ミリモル)及び200μLのEt3Nの溶液を、10mLのトルエン中の[(R)−(ビフェン)]PBr(529mg、1.22ミリモル)の溶液に添加した。この溶液を環境温度で2時間攪拌し、次いで濾過した。濾液を蒸発させて白色固体にした(0.506g、収率97%)。NMRキャラクタリゼーションによって、この生成物が、構造:
15mLのトルエン中のカテコール(169mg、1.53ミリモル)及び460μLのEt3Nの溶液を、10mLのトルエン中の[(R)−(ビフェン)]PBr(1.329g、3.07ミリモル)の溶液に添加した。この溶液を環境温度で18時間攪拌し、次いで濾過した。濾液を蒸発させて白色固体にし、これをアセトニトリルと共にすりつぶした。得られた白色固体を真空下で乾燥させた(0.779g、収率58%)。NMRキャラクタリゼーションによって、この生成物が、構造:
4mLの、N,N’−ジメチル−N,N’−ビス−トリメチルシラニル−プロパン−1,3−ジアミン(83.8mg、0.34ミリモル)のトルエン溶液に、347mg(0.68ミリモル)の(R−ビフェン)PI(トルエン中の(R−ビフェン)PBrとMe3SiIとの反応によって製造した)を添加した。この溶液を18時間攪拌した。この溶液を約2mLにまで濃縮し、続いて4mLのヘキサンを添加した。30分間攪拌した後、濾過によって白色固体を集めた。この固体を減圧下で乾燥させて、246mg(収率83%)の生成物を得た。31P{1H}(C6D6)δ140.9。NMRキャラクタリゼーションによって、この生成物が、構造:
(S)−(3,3’−Me3Si−ビノール)PBrを4mLのトルエン中に溶解させた。N,N’−ジメチル−N,N’−ビス−トリメチルシラニル−プロパン−1,3−ジアミンを添加した。この反応物を18時間攪拌し、次いで、溶媒を除去して、0.359mgの生成物を灰白色固体として残した。収率101.6%。31P{1H}(C6D6)δ149.5。NMRキャラクタリゼーションによって、この生成物が、構造:
これらの実施例は、全て、同じ一般的手順を使用して実施した。窒素雰囲気下で、Rh(CO)2(acac)(5.6mg、0.022ミリモル)及び試験すべき配位子(1.1当量/Rh)を、アセトン(5mL)中に溶解させた。得られた溶液に、0.5mLのアルケンを添加した。この溶液を8本の平行な機械式攪拌付き圧力反応器からなる反応器システムに移した。この平行反応器は、それぞれ個々の温度及び圧力コントロールを有している。それぞれの反応器の全体積は15mLである。触媒溶液を装入して、反応器を所望の温度まで加熱し、次いで、150psiの1:1 H2/COで加圧した。反応物を一定圧力下で3時間攪拌し、その後、反応器を大気圧に開放した。次いで、キラル固定相ガスクロマトグラフィーによる分析のために、サンプルを取り出した。酢酸ビニルヒドロホルミル化サンプルを、エナンチオマー過剰(%ee)及び位置選択率(b/l)の決定のために、2−アセトキシプロピオンアルデヒド及び3−アセトキシプロピオンアルデヒドのエナンチオマーを分割することができた、スペルコ(Supelco)BETA Dex−225(30m×0.25mm、250μm膜厚さ)カラムを使用して分析した。シアン化アリルヒドロホルミル化サンプルを、エナンチオマー過剰(%ee)及び位置選択率(b/l)の決定のために、3−ホルミルブチロニトリル及び4−ホルミルブチロニトリルのエナンチオマーを分割することができた、キラルデックス(Chiraldex)A−TA(30m×0.25mm、250μm膜厚さ)カラムを使用して分析した。これらのデータを、表I及び表IIに示す。
窒素雰囲気下で、Rh(CO)2(acac)(5.6mg、0.022ミリモル)及びキラファイト(1.1当量/Rh)を、アセトン(5mL)中に溶解させた。得られた溶液に、0.5mLのアルケンを添加した。この溶液を8本の平行な機械式攪拌付き圧力反応器の1個の中に移した。触媒溶液を装入して、反応器を所望の温度まで加熱し、次いで、150psiの1:1 H2/COで加圧した。反応物を一定圧力下で3時間攪拌し、その後、反応器を大気圧に開放した。次いで、キラル固定相ガスクロマトグラフィーによる分析のために、サンプルを取り出した。酢酸ビニルヒドロホルミル化サンプルを、エナンチオマー過剰(%ee)及び位置選択率(b/l)の決定のために、2−アセトキシプロピオンアルデヒド及び3−アセトキシプロピオンアルデヒドのエナンチオマーを分割することができた、スペルコBETA Dex−225(30m×0.25mm、250μm膜厚さ)カラムを使用して分析した。シアン化アリルヒドロホルミル化サンプルを、エナンチオマー過剰(%ee)及び位置選択率(b/l)の決定のために、3−ホルミルブチロニトリル及び4−ホルミルブチロニトリルのエナンチオマーを分割することができた、キラルデックスA−TA(30m×0.25mm、250μm膜厚さ)カラムを使用して分析した。これらのデータを、表1及び表2に示す。
窒素雰囲気下で、Rh(CO)2(acac)(5.6mg、0.022ミリモル)及びビナホス(1.1当量/Rh)を、アセトン(5mL)中に溶解させた。得られた溶液に、0.5mLのアルケンを添加した。この溶液を8本の平行な機械式攪拌付き圧力反応器の1個の中に移した。触媒溶液を装入して、反応器を所望の温度まで加熱し、次いで、150psiの1:1 H2/COで加圧した。反応物を一定圧力下で3時間攪拌し、その後、反応器を大気圧に開放した。次いで、キラル固定相ガスクロマトグラフィーによる分析のために、サンプルを取り出した。酢酸ビニルヒドロホルミル化サンプルを、エナンチオマー過剰(%ee)及び位置選択率(b/l)の決定のために、2−アセトキシプロピオンアルデヒド及び3−アセトキシプロピオンアルデヒドのエナンチオマーを分割することができた、スペルコBETA Dex−225(30m×0.25mm、250μm膜厚さ)カラムを使用して分析した。シアン化アリルヒドロホルミル化サンプルを、エナンチオマー過剰(%ee)及び位置選択率(b/l)の決定のために、3−ホルミルブチロニトリル及び4−ホルミルブチロニトリルのエナンチオマーを分割することができた、キラルデックスA−TA(30m×0.25mm、250μm膜厚さ)カラムを使用して分析した。これらのデータを、表I及び表IIに示す。
25mLの機械式攪拌付きオートクレーブに、Rh(CO)2(acac)(31.6mg、0.122ミリモル)及びビスホスファイトI(159mg、0.167ミリモル)を装入した。シアン化アリルを、溶解した酸素を除去するために窒素で散布し、そしてオートクレーブに添加した。反応器を1:1 H2/COでフラッシュし、次いで108psiaに加圧した。この反応混合物を108psiaのH2/CO下で18時間30℃で攪拌した。キラルデックスA−TA(30m×0.25mm、250μm膜厚さ)カラムを使用するキラルGC分析によって、79%ee及び19:1b/lでの完全な転化が示された。
窒素雰囲気下で、Rh(CO)2(acac)(5.6mg、0.022ミリモル)及びビスホスファイトI(29.2mg、0.031ミリモル)を、アセトン(5mL)中に溶解させた。得られた溶液に、0.5mLのクロトニトリルを添加した。この溶液を、8本の平行な機械式攪拌付き圧力反応器の1個に移した。反応器を30℃まで加熱し、次いで150psiの1:1 H2/COで加圧した。反応物を一定圧力下で3時間攪拌し、その後、反応器を大気圧に開放した。キラルデックスA−TA(30m×0.25mm、250μm膜厚さ)カラムを使用するキラルGC分析によって、75%eeでの3−ホルミルブチロニトリルの生成が示された。GCによって、直鎖位置異性体は検出されなかった。
Claims (44)
- プロキラル又はキラルオレフィン性不飽和有機化合物を、一酸化炭素及び水素と、光学活性金属−配位子錯体触媒の存在下に、反応させて、光学活性アルデヒド生成物を製造することを含んでなるヒドロホルミル化方法であって、前記光学活性金属−配位子錯体触媒が式:
を有する光学的に活性な配位子で錯化された金属を含んでなるヒドロホルミル化方法。それぞれのWが酸素である、請求項1に記載の方法。 - それぞれのYが、同じものであり、そして、第三級アルキル、トリアルキルシリル及びアリールから選択された置換基である請求項1に記載の方法。
- それぞれのYが第三級アルキルである請求項1に記載の方法。
- それぞれのYがt−ブチルである請求項1に記載の方法。
- W−X−Wが2,2’−ジヒドロキシビフェニルから誘導される請求項1に記載の方法。
- Yがt−ブチルであり、W−X−Wが2,2’−ジヒドロキシビフェニルから誘導され、そしてZ及びZ’がメチルである請求項1に記載の方法。
- 光学活性金属−配位子錯体中の金属が第VIII族、第IB族及び第VIB族金属から選択される請求項1に記載の方法。
- 光学活性金属−配位子錯体中の金属が第VIII族金属である請求項1に記載の方法。
- 第VIII族金属がロジウム(Rh)、コバルト(Co)、イリジウム(Ir)、ルテニウム(Ru)、鉄(Fe)、ニッケル(Ni)、パラジウム(Pd)、白金(Pt)、オスミウム(Os)及びこれらの混合物から選択される請求項1に記載の方法。
- 第VIII族金属がロジウムである請求項1に記載の方法。
- 光学活性金属−配位子錯体触媒が一酸化炭素で更に錯化されている請求項1に記載の方法。
- 添加された遊離配位子の存在下で実施する請求項1に記載の方法。
- プロキラル又はキラルオレフィン性不飽和有機化合物が置換又は非置換のオレフィンを含む請求項1に記載の方法。
- 置換又は非置換のオレフィンがp−イソブチルスチレン、2−ビニル−6−メトキシナフチレン、3−エテニルフェニルフェニルケトン、4−エテニルフェニル−2−チエニルケトン、4−エテニル−2−フルオロビフェニル、4−(1,3−ジヒドロ−1−オキソ−2H−イソインドール−2−イル)スチレン、2−エテニル−5−ベンゾイルチオフェン、3−エテニルフェニルフェニルエーテル、プロペニルベンゼン、イソブチル−4−プロペニルベンゼン、フェニルビニルエーテル、シアン化アリル、酢酸ビニル、クロトニトリル、α−(p−トリフルオロメチルフェノキシ)スチレン又は塩化ビニルからなる群から選択される請求項1に記載の方法。
- オレフィンがシアン化アリルである請求項1に記載の方法。
- オレフィンが酢酸ビニルである請求項1に記載の方法。
- オレフィンがクロトニトリルである請求項1に記載の方法。
- 光学活性生成物が50%よりも大きいエナンチオマー過剰を有する請求項1に記載の方法。
- 光学活性生成物が75%よりも大きいエナンチオマー過剰を有する請求項1に記載の方法。
- 光学活性生成物が90%よりも大きいエナンチオマー過剰を有する請求項1に記載の方法。
- キラルオレフィン性不飽和有機化合物がモノ置換された末端オレフィンであり、そして分枝鎖生成物の直鎖生成物に対する比が4:1よりも大きい請求項1に記載の方法。
- キラルオレフィン性不飽和有機化合物がモノ置換された末端オレフィンであり、そして分枝鎖生成物の直鎖生成物に対する比が10:1よりも大きい請求項1に記載の方法。
- キラルオレフィン性不飽和有機化合物がモノ置換された末端オレフィンであり、そして分枝鎖生成物の直鎖生成物に対する比が20:1よりも大きい請求項1に記載の方法。
- 更に、光学活性生成物を誘導することを更に含む請求項1に記載の方法。
- 光学活性生成物を誘導することを更に含み、その誘導反応が酸化、還元、縮合、アミノ化、エステル化、アルキル化又はアシル化反応を含む請求項1に記載の方法。
- Wが酸素である請求項30に記載の配位子。
- それぞれのYが、同じものであり、そして、第三級アルキル、トリアルキルシリル及びアリールから選択された置換基である請求項30に記載の配位子。
- それぞれのYが第三級アルキルである請求項31に記載の配位子。
- それぞれのYがt−ブチルである請求項30に記載の配位子。
- W−X−Wが2,2’−ジヒドロキシビフェニルから誘導される請求項30に記載の配位子。
- Yがt−ブチルであり、W−X−Wが2,2’−ジヒドロキシビフェニルから誘導され、そしてZ及びZ’がメチルである請求項30に記載の配位子。
- 式:
を有する光学活性配位子で錯化された金属を含む光化学活性金属−配位子錯体触媒。 - 金属が第VIII族、第IB族及び第VIB族金属から選択される請求項37に記載の光学活性金属−配位子錯体触媒。
- 金属が第VIII族金属である請求項37に記載の光学活性金属−配位子錯体触媒。
- 金属がロジウム(Rh)、コバルト(Co)、イリジウム(Ir)、ルテニウム(Ru)、鉄(Fe)、ニッケル(Ni)、パラジウム(Pd)、白金(Pt)、オスミウム(Os)及びこれらの混合物から選択された第VIII族金属である請求項37に記載の光学活性金属−配位子錯体触媒。
- 金属がロジウムである請求項37に記載の光学活性金属−配位子錯体触媒。
- 一酸化炭素で更に錯化されている請求項37に記載の光学活性金属−配位子錯体触媒。
- (i)請求項30に記載の式を有する光学活性配位子で錯化された金属を含む光学活性金属−配位子錯体触媒、(ii)有機溶媒及び(iii)請求項29に記載の遊離配位子を含む光学活性金属−配位子錯体触媒前駆体組成物。
- 請求項1に記載の方法によって製造された光学活性生成物。
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US10/401,464 US7015360B2 (en) | 2003-03-28 | 2003-03-28 | Asymmetric catalysts prepared from optically active bisphosphites bridged by achiral diols |
PCT/US2004/006291 WO2004094442A2 (en) | 2003-03-28 | 2004-03-02 | Asymmetric catalysts prepared from optically active bisphosphites bridged by achiral diols |
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US (1) | US7015360B2 (ja) |
EP (1) | EP1611145A2 (ja) |
JP (1) | JP2006521385A (ja) |
CN (1) | CN1768070B (ja) |
WO (1) | WO2004094442A2 (ja) |
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JPWO2005090369A1 (ja) * | 2004-03-23 | 2008-01-31 | 株式会社クラレ | ビスホスファイトおよび該ビスホスファイトを用いたアルデヒド化合物の製造方法 |
JP2010024228A (ja) * | 2008-06-20 | 2010-02-04 | Mitsubishi Chemicals Corp | リン化合物の製造方法及びアリル化合物誘導体の製造方法 |
JP2014169346A (ja) * | 2007-11-06 | 2014-09-18 | Mitsubishi Chemicals Corp | 遷移金属錯体と芳香族ホスファイトの混合溶液 |
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DE10352757A1 (de) * | 2003-11-12 | 2005-06-16 | Studiengesellschaft Kohle Mbh | Chirale Di- und Triphosphite |
DE602005004162T2 (de) * | 2004-08-27 | 2008-05-08 | The Dow Chemical Company, Midland | Neuartige diazaphospholan-liganden für asymmetrische katalysatoren |
JP4928798B2 (ja) * | 2005-02-17 | 2012-05-09 | 独立行政法人科学技術振興機構 | 不斉合成用触媒およびそれに用いる配位子、並びにこれらを用いた不斉合成反応による光学活性化合物の製造方法 |
DE102005025797A1 (de) * | 2005-06-02 | 2006-12-07 | Studiengesellschaft Kohle Mbh | Chirale Diphosphonite als Liganden in der ruthenium-katalysierten enantioselektiven Reduktion von Ketonen, β-Ketoestern und Ketiminen |
DE102005044355A1 (de) * | 2005-09-16 | 2007-03-22 | Studiengesellschaft Kohle Mbh | Chirale Phosphoramidite |
BRPI0619982A2 (pt) * | 2005-12-15 | 2011-10-25 | The Penn State Research Foundation | ligantes de tetrafósforo para hidroformilação catalìtica e reações relacionadas |
KR100913489B1 (ko) * | 2006-06-29 | 2009-08-25 | 주식회사 엘지화학 | 인 화합물을 포함하는 촉매 조성물 및 이를 이용한히드로포르밀화 반응 |
US9499463B2 (en) * | 2012-10-12 | 2016-11-22 | Evonik Degussa Gmbh | Mixtures of constitutionally isomeric bisphosphites |
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US20230043867A1 (en) * | 2019-12-09 | 2023-02-09 | Wanhua Chemical Group Co., Ltd. | Preparation method for optically active citronellal |
CN110872217A (zh) * | 2019-12-09 | 2020-03-10 | 万华化学集团股份有限公司 | 一种光学活性的香茅醛的制备方法 |
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CN111056933B (zh) * | 2019-12-24 | 2022-11-08 | 万华化学集团股份有限公司 | 一种制备光学活性香茅醛的方法及用于该方法的催化剂体系 |
CN111203277B (zh) * | 2020-02-27 | 2022-11-18 | 郑州大学 | 手性双齿亚磷酸酯配体的应用、Conia-Ene反应催化剂和构建手性季碳中心的方法 |
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JPWO2005090369A1 (ja) * | 2004-03-23 | 2008-01-31 | 株式会社クラレ | ビスホスファイトおよび該ビスホスファイトを用いたアルデヒド化合物の製造方法 |
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JP2010024228A (ja) * | 2008-06-20 | 2010-02-04 | Mitsubishi Chemicals Corp | リン化合物の製造方法及びアリル化合物誘導体の製造方法 |
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CN1768070B (zh) | 2012-07-11 |
CN1768070A (zh) | 2006-05-03 |
WO2004094442A3 (en) | 2005-02-10 |
US7015360B2 (en) | 2006-03-21 |
US20040199023A1 (en) | 2004-10-07 |
WO2004094442A2 (en) | 2004-11-04 |
EP1611145A2 (en) | 2006-01-04 |
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