JP6261563B2 - 光学活性アルデヒドの製造方法 - Google Patents
光学活性アルデヒドの製造方法 Download PDFInfo
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- JP6261563B2 JP6261563B2 JP2015504378A JP2015504378A JP6261563B2 JP 6261563 B2 JP6261563 B2 JP 6261563B2 JP 2015504378 A JP2015504378 A JP 2015504378A JP 2015504378 A JP2015504378 A JP 2015504378A JP 6261563 B2 JP6261563 B2 JP 6261563B2
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- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 title claims description 20
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- -1 dialkylammonium ion Chemical class 0.000 claims description 174
- 125000004432 carbon atom Chemical group C* 0.000 claims description 59
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 54
- 125000001424 substituent group Chemical group 0.000 claims description 44
- 239000003446 ligand Substances 0.000 claims description 41
- 125000003118 aryl group Chemical group 0.000 claims description 33
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 28
- 229910052801 chlorine Inorganic materials 0.000 claims description 25
- 229910052740 iodine Inorganic materials 0.000 claims description 25
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 24
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 24
- 125000005843 halogen group Chemical group 0.000 claims description 22
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 17
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 14
- 239000012327 Ruthenium complex Substances 0.000 claims description 14
- 125000004423 acyloxy group Chemical group 0.000 claims description 14
- 150000001450 anions Chemical class 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 11
- 125000002723 alicyclic group Chemical group 0.000 claims description 10
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 150000001993 dienes Chemical class 0.000 claims description 9
- 125000003342 alkenyl group Chemical group 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims description 3
- 229910052770 Uranium Inorganic materials 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- 125000000129 anionic group Chemical group 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 description 26
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 20
- 150000001875 compounds Chemical class 0.000 description 20
- HFPZCAJZSCWRBC-UHFFFAOYSA-N p-cymene Chemical compound CC(C)C1=CC=C(C)C=C1 HFPZCAJZSCWRBC-UHFFFAOYSA-N 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 18
- 239000000460 chlorine Substances 0.000 description 17
- 125000003545 alkoxy group Chemical group 0.000 description 16
- 125000003277 amino group Chemical group 0.000 description 16
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 14
- 239000003054 catalyst Substances 0.000 description 11
- 125000000623 heterocyclic group Chemical group 0.000 description 11
- 238000006317 isomerization reaction Methods 0.000 description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 11
- 230000003287 optical effect Effects 0.000 description 11
- IWSZDQRGNFLMJS-UHFFFAOYSA-N 2-(dibutylamino)ethanol Chemical compound CCCCN(CCO)CCCC IWSZDQRGNFLMJS-UHFFFAOYSA-N 0.000 description 10
- GLZPCOQZEFWAFX-UHFFFAOYSA-N Geraniol Chemical compound CC(C)=CCCC(C)=CCO GLZPCOQZEFWAFX-UHFFFAOYSA-N 0.000 description 10
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 10
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 10
- 239000000758 substrate Substances 0.000 description 10
- ASNHGEVAWNWCRQ-UHFFFAOYSA-N 4-(hydroxymethyl)oxolane-2,3,4-triol Chemical compound OCC1(O)COC(O)C1O ASNHGEVAWNWCRQ-UHFFFAOYSA-N 0.000 description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 101001095088 Homo sapiens Melanoma antigen preferentially expressed in tumors Proteins 0.000 description 9
- 102100037020 Melanoma antigen preferentially expressed in tumors Human genes 0.000 description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 9
- 239000002585 base Substances 0.000 description 8
- 125000004122 cyclic group Chemical group 0.000 description 8
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 8
- 229910052731 fluorine Inorganic materials 0.000 description 8
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 8
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 8
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 8
- 125000003506 n-propoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 8
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 8
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 8
- XOTOKOVCCBSUNT-UHFFFAOYSA-N 4-methyl-3-phenylpentan-1-ol Chemical compound OCCC(C(C)C)C1=CC=CC=C1 XOTOKOVCCBSUNT-UHFFFAOYSA-N 0.000 description 7
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 7
- IOPQYDKQISFMJI-UHFFFAOYSA-N [1-[2-bis(4-methylphenyl)phosphanylnaphthalen-1-yl]naphthalen-2-yl]-bis(4-methylphenyl)phosphane Chemical compound C1=CC(C)=CC=C1P(C=1C(=C2C=CC=CC2=CC=1)C=1C2=CC=CC=C2C=CC=1P(C=1C=CC(C)=CC=1)C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 IOPQYDKQISFMJI-UHFFFAOYSA-N 0.000 description 7
- 238000004817 gas chromatography Methods 0.000 description 7
- 125000005842 heteroatom Chemical group 0.000 description 7
- 125000006606 n-butoxy group Chemical group 0.000 description 7
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 7
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 6
- GLZPCOQZEFWAFX-YFHOEESVSA-N Geraniol Natural products CC(C)=CCC\C(C)=C/CO GLZPCOQZEFWAFX-YFHOEESVSA-N 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Natural products OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 6
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 125000002510 isobutoxy group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])O* 0.000 description 6
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 6
- VYMDGNCVAMGZFE-UHFFFAOYSA-N phenylbutazonum Chemical compound O=C1C(CCCC)C(=O)N(C=2C=CC=CC=2)N1C1=CC=CC=C1 VYMDGNCVAMGZFE-UHFFFAOYSA-N 0.000 description 6
- 125000003367 polycyclic group Chemical group 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 229910052707 ruthenium Inorganic materials 0.000 description 6
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 5
- 150000001555 benzenes Chemical group 0.000 description 5
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 5
- 229910052794 bromium Inorganic materials 0.000 description 5
- 125000000753 cycloalkyl group Chemical group 0.000 description 5
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 5
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 125000002950 monocyclic group Chemical group 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 125000005561 phenanthryl group Chemical group 0.000 description 5
- 125000004076 pyridyl group Chemical group 0.000 description 5
- 125000005920 sec-butoxy group Chemical group 0.000 description 5
- 229910006384 μ-Br Inorganic materials 0.000 description 5
- 229910006400 μ-Cl Inorganic materials 0.000 description 5
- DODDFEFVZYZASI-XYOKQWHBSA-N (e)-4-methyl-3-phenylpent-2-en-1-ol Chemical compound OC\C=C(C(C)C)\C1=CC=CC=C1 DODDFEFVZYZASI-XYOKQWHBSA-N 0.000 description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- 229910020366 ClO 4 Inorganic materials 0.000 description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 4
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 4
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 4
- 229910018286 SbF 6 Inorganic materials 0.000 description 4
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 4
- 125000005103 alkyl silyl group Chemical group 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 4
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 4
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 4
- LJSQFQKUNVCTIA-UHFFFAOYSA-N diethyl sulfide Chemical compound CCSCC LJSQFQKUNVCTIA-UHFFFAOYSA-N 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 125000001153 fluoro group Chemical group F* 0.000 description 4
- 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 4
- 150000002430 hydrocarbons Chemical group 0.000 description 4
- 239000011630 iodine Substances 0.000 description 4
- 125000001624 naphthyl group Chemical group 0.000 description 4
- 125000001181 organosilyl group Chemical class [SiH3]* 0.000 description 4
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 4
- 125000000587 piperidin-1-yl group Chemical group [H]C1([H])N(*)C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 4
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 4
- 125000002112 pyrrolidino group Chemical group [*]N1C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 4
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 4
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 4
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 4
- XOTOKOVCCBSUNT-GFCCVEGCSA-N (3R)-4-methyl-3-phenylpentan-1-ol Chemical compound C1(=CC=CC=C1)[C@H](CCO)C(C)C XOTOKOVCCBSUNT-GFCCVEGCSA-N 0.000 description 3
- GLZPCOQZEFWAFX-JXMROGBWSA-N (E)-Geraniol Chemical compound CC(C)=CCC\C(C)=C\CO GLZPCOQZEFWAFX-JXMROGBWSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 3
- RGHNJXZEOKUKBD-SQOUGZDYSA-M D-gluconate Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O RGHNJXZEOKUKBD-SQOUGZDYSA-M 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical group CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000002252 acyl group Chemical class 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 125000005104 aryl silyl group Chemical group 0.000 description 3
- 229940077388 benzenesulfonate Drugs 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 125000001231 benzoyloxy group Chemical group C(C1=CC=CC=C1)(=O)O* 0.000 description 3
- MUALRAIOVNYAIW-UHFFFAOYSA-N binap Chemical group C1=CC=CC=C1P(C=1C(=C2C=CC=CC2=CC=1)C=1C2=CC=CC=C2C=CC=1P(C=1C=CC=CC=1)C=1C=CC=CC=1)C1=CC=CC=C1 MUALRAIOVNYAIW-UHFFFAOYSA-N 0.000 description 3
- 229940063013 borate ion Drugs 0.000 description 3
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 3
- XTEGARKTQYYJKE-UHFFFAOYSA-M chlorate Inorganic materials [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 3
- PMOWTIHVNWZYFI-WAYWQWQTSA-N cis-2-coumaric acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1O PMOWTIHVNWZYFI-WAYWQWQTSA-N 0.000 description 3
- 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 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
- 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 3
- 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 3
- 125000004663 dialkyl amino group Chemical group 0.000 description 3
- 235000011180 diphosphates Nutrition 0.000 description 3
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 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 3
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 3
- ICIWUVCWSCSTAQ-UHFFFAOYSA-M iodate Chemical compound [O-]I(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-M 0.000 description 3
- 229940005633 iodate ion Drugs 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
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 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
- 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
- 229940005654 nitrite ion Drugs 0.000 description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 3
- 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 3
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 229940049964 oleate Drugs 0.000 description 3
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- SCZVXVGZMZRGRU-UHFFFAOYSA-N n'-ethylethane-1,2-diamine Chemical group CCNCCN SCZVXVGZMZRGRU-UHFFFAOYSA-N 0.000 description 1
- KFIGICHILYTCJF-UHFFFAOYSA-N n'-methylethane-1,2-diamine Chemical group CNCCN KFIGICHILYTCJF-UHFFFAOYSA-N 0.000 description 1
- AHSQQFCXXXKGLE-UHFFFAOYSA-N n'-tert-butyl-1-phenylethane-1,2-diamine Chemical compound CC(C)(C)NCC(N)C1=CC=CC=C1 AHSQQFCXXXKGLE-UHFFFAOYSA-N 0.000 description 1
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 description 1
- 125000004593 naphthyridinyl group Chemical group N1=C(C=CC2=CC=CN=C12)* 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000001196 nonadecyl 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])C([H])([H])[H] 0.000 description 1
- 125000005187 nonenyl group Chemical group C(=CCCCCCCC)* 0.000 description 1
- 125000005064 octadecenyl group Chemical group C(=CCCCCCCCCCCCCCCCC)* 0.000 description 1
- 125000004365 octenyl group Chemical group C(=CCCCCCC)* 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 125000000466 oxiranyl group Chemical group 0.000 description 1
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 125000000913 palmityl 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])[H] 0.000 description 1
- 125000002958 pentadecyl 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])[H] 0.000 description 1
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 1
- 125000006678 phenoxycarbonyl group Chemical group 0.000 description 1
- RCIBIGQXGCBBCT-UHFFFAOYSA-N phenyl isocyanide Chemical compound [C-]#[N+]C1=CC=CC=C1 RCIBIGQXGCBBCT-UHFFFAOYSA-N 0.000 description 1
- 125000004344 phenylpropyl group Chemical group 0.000 description 1
- GTBPUYSGSDIIMM-UHFFFAOYSA-N phosphane;ruthenium Chemical compound P.[Ru] GTBPUYSGSDIIMM-UHFFFAOYSA-N 0.000 description 1
- 150000003002 phosphanes Chemical class 0.000 description 1
- VXTFGYMINLXJPW-UHFFFAOYSA-N phosphinane Chemical compound C1CCPCC1 VXTFGYMINLXJPW-UHFFFAOYSA-N 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- GWLJTAJEHRYMCA-UHFFFAOYSA-N phospholane Chemical compound C1CCPC1 GWLJTAJEHRYMCA-UHFFFAOYSA-N 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 125000004592 phthalazinyl group Chemical group C1(=NN=CC2=CC=CC=C12)* 0.000 description 1
- 125000004193 piperazinyl group Chemical group 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 125000001501 propionyl group Chemical group O=C([*])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
- 125000005412 pyrazyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 125000002294 quinazolinyl group Chemical group N1=C(N=CC2=CC=CC=C12)* 0.000 description 1
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 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
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000000243 solution Substances 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
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000005063 tetradecenyl group Chemical group C(=CCCCCCCCCCCCC)* 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000003718 tetrahydrofuranyl group Chemical group 0.000 description 1
- 125000001412 tetrahydropyranyl group Chemical group 0.000 description 1
- 125000005958 tetrahydrothienyl group Chemical group 0.000 description 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000005247 tetrazinyl group Chemical group N1=NN=NC(=C1)* 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 125000004665 trialkylsilyl group Chemical group 0.000 description 1
- NVLRFXKSQQPKAD-UHFFFAOYSA-N tricarbon Chemical compound [C]=C=[C] NVLRFXKSQQPKAD-UHFFFAOYSA-N 0.000 description 1
- 125000005040 tridecenyl group Chemical group C(=CCCCCCCCCCCC)* 0.000 description 1
- 125000002889 tridecyl 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])[H] 0.000 description 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 description 1
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 description 1
- 125000005065 undecenyl group Chemical group C(=CCCCCCCCCC)* 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
- C07C45/511—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups
- C07C45/512—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups the singly bound functional group being a free hydroxyl group
-
- 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
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/07—Optical isomers
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
また、非特許文献5〜16に記載されたロジウム、ルテニウム等の遷移金属錯体を用いた方法が知られている。しかしながら、これらの方法は、基質特異性が高く、汎用的な方法であるとはいえなかった。
このため、従来より、光学活性アルデヒドを製造するための一般性の高い、しかも高選択的、高収率で製造できる、新しい合成方法の実現が望まれていた。
すなわち、本発明は、簡単で工程数が少なく、高い光学純度で、より安価、高収率で光学活性アルデヒドを製造することを可能とするものである。
[1] 式(1)
で表される光学活性アルデヒドの製造方法であって、
式(2)
で表されるアリルアルコールを、ルテニウム錯体と塩基の存在下に不斉異性化することを特徴とする、製造方法。
[RumLnWpUq]rZs (3)
(式(3)中、Lは、光学活性ホスフィン配位子であり;Wは、水素原子、ハロゲン原子、アシルオキシ基、アリール基、ジエン又はアニオンであり;Uは、水素原子、ハロゲン原子、アシルオキシ基、アリール基、ジエン、アニオン又はL以外の配位子であり;Zは、アニオン、アミン又は光学活性含窒素化合物であり;m、n及びrは各々独立に1〜5の整数であり、p、q及びsは各々独立に0〜5の整数であり、p+q+sは1以上である。)
で表されるルテニウム錯体を用いて行なうことを特徴とする、上記[1]に記載の製造方法。
本発明の光学活性アルヒデドを製造する方法は、以下に示される反応にしたがって、行われる。
これらはいずれも、その分子内に二重結合が存在するため、(E)−体および(Z)−体の幾何異性体が存在するが、本発明で行われる不斉異性化反応に用いる場合は、(E)−体および(Z)−体を単独で用いられる。
より具体的に説明すると、本発明で用いられる不斉配位子は、例えば、単座配位子、二座配位子、三座配位子、四座配位子等が挙げられる。例えば、光学活性ホスフィン化合物、光学活性アミン化合物、光学活性アルコール化合物、光学活性硫黄化合物、光学活性カルベン化合物等が挙げられる。好ましくは、光学活性ホスフィン化合物が挙げられる。
で表される光学活性二座ホスフィン配位子が挙げられる。
特に好ましいR10及びR11としては、水素原子、メトキシ基が挙げられる。
特に好ましいR12としては、メチル基、メトキシ基が挙げられる。
[RumLnWpUq]rZs (3)
(式中、Lは、光学活性ホスフィン配位子であり;Wは、水素原子、ハロゲン原子、アシルオキシ基、アリール基、ジエン又はアニオンであり;Uは、水素原子、ハロゲン原子、アシルオキシ基、アリール基、ジエン、アニオン又はL以外の配位子であり;Zは、アニオン、アミン又は光学活性含窒素化合物であり;m、n及びrは各々独立に1〜5の整数をであり、p、q及びsは各々独立に0〜5の整数であり、p+q+sは1以上である。)
一般式(3)のWで表されるハロゲン原子としては、例えば、フッ素原子、塩素原子、臭素原子、ヨウ素原子が挙げられる。
一般式(3)のWで表されるアシルオキシ基としては、例えば、フォルミルオキシ基、アセトキシ基、プロピオニルオキシ基、ブチルオキシ基、ベンゾイルオキシ基等が挙げられる。
一般式(3)のWで表されるアリール基としては、例えば、フェニル基、ナフチル基、アントラニル基、フェナントリル基、インデニル基、メシチル基、ジベンジル基等の芳香族単環、多環式基等が挙げられる。
一般式(3)のWで表されるジエンとしては、例えば、ブタジエン、シクロオクタジエン(cod)、ノルボルナジエン(nod)等が挙げられる。
一般式(3)のWで表されるアニオンとしては、例えば、硝酸イオン、亜硝酸イオン、硫酸イオン、亜硫酸イオン、スルホン酸イオン(メタンスルホン酸イオン、ベンゼンスルホン酸イオン、p−トルエンスルホン酸イオン、カンフルスルホン酸イオン、トリフルオロメタンスルホン酸イオンなど)、スルファミン酸イオン、炭酸イオン、水酸化物イオン、カルボン酸イオン(ギ酸イオン、酢酸イオン、プロピオン酸イオン、グルコン酸イオン、オレイン酸イオン、シュウ酸イオン、安息香酸イオン、フタル酸イオン、トリフルオロ酢酸イオンなど)、硫化物イオン、チオシアン酸イオン、リン酸イオン、ピロリン酸イオン、酸化物イオン、リン化物イオン、塩素酸イオン、過塩素酸イオン、ヨウ素酸イオン、ヘキサフルオロケイ酸イオン、シアン化物イオン、ホウ酸イオン、メタホウ酸イオン、ホウフッ化物イオン等が挙げられる。
一般式(3)のUで表されるハロゲン原子としては、例えば、フッ素原子、塩素原子、臭素原子、ヨウ素原子が挙げられる。
一般式(3)のUで表されるアシルオキシ基としては、例えば、フォルミルオキシ基、アセトキシ基、プロピオニルオキシ基、ブチルオキシ基、ベンゾイルオキシ基等が挙げられる。
一般式(3)のUで表されるアリール基としては、例えば、フェニル基、ナフチル基、アントラニル基、フェナントリル基、インデニル基、メシチル基、ジベンジル基等の芳香族単環、多環式基等が挙げられる。
一般式(3)のUで表されるジエンとしては、例えば、ブタジエン、シクロオクタジエン(cod)、ノルボルナジエン(nod)等が挙げられる。
一般式(3)のUで表されるアニオンとしては、例えば、硝酸イオン、亜硝酸イオン、硫酸イオン、亜硫酸イオン、スルホン酸イオン(メタンスルホン酸イオン、ベンゼンスルホン酸イオン、p−トルエンスルホン酸イオン、カンフルスルホン酸イオン、トリフルオロメタンスルホン酸イオンなど)、スルファミン酸イオン、炭酸イオン、水酸化物イオン、カルボン酸イオン(ギ酸イオン、酢酸イオン、プロピオン酸イオン、グルコン酸イオン、オレイン酸イオン、シュウ酸イオン、安息香酸イオン、フタル酸イオン、トリフルオロ酢酸イオンなど)、硫化物イオン、チオシアン酸イオン、リン酸イオン、ピロリン酸イオン、酸化物イオン、リン化物イオン、塩素酸イオン、過塩素酸イオン、ヨウ素酸イオン、ヘキサフルオロケイ酸イオン、シアン化物イオン、ホウ酸イオン、メタホウ酸イオン、ホウフッ化物イオン等が挙げられる。
一般式(3)のZで表されるアニオンとしては、例えば、硝酸イオン、亜硝酸イオン、硫酸イオン、亜硫酸イオン、スルホン酸イオン(メタンスルホン酸イオン、ベンゼンスルホン酸イオン、p−トルエンスルホン酸イオン、カンフルスルホン酸イオン、トリフルオロメタンスルホン酸イオンなど)、スルファミン酸イオン、炭酸イオン、水酸化物イオン、カルボン酸イオン(ギ酸イオン、酢酸イオン、プロピオン酸イオン、グルコン酸イオン、オレイン酸イオン、シュウ酸イオン、安息香酸イオン、フタル酸イオン、トリフルオロ酢酸イオンなど)、硫化物イオン、チオシアン酸イオン、リン酸イオン、ピロリン酸イオン、酸化物イオン、リン化物イオン、塩素酸イオン、過塩素酸イオン、ヨウ素酸イオン、ヘキサフルオロケイ酸イオン、シアン化物イオン、ホウ酸イオン、メタホウ酸イオン、ホウフッ化物イオン等が挙げられる。
一般式(3)のZで表されるアミンとしては、メチルアミン、エチルアミン、n−プロピルアミン、イソプロピルアミン、n−ブチルアミン、s−ブチルアミン、tert−ブチルアミン、シクロヘキシルアミン等の脂肪族アミン類;アニリン、ジメチルアニリン等の芳香族アミン類;ピリジン(py)、ジメチルアミノピリジン等の含窒素芳香族複素環類、ピロリジン、ピペラジン等の含窒素脂肪族複素環類;エチレンジアミン(en)、プロピレンジアミン、トリエチレンジアミン、テトラメチルエチレンジアミン(TMEDA)、ビピリジン(bpy)、フェナントロリン(phen)等のジアミン類)、硫黄化合物(ジメチルスルフィド、ジエチルスルフィド、ジプロピルスルフィド、ジブチルスルフィド等)等を挙げることができる。
一般式(3)のZで表される光学活性含窒素化合物としては、次の一般式(6);
例えば光学活性な1,2−ジフェニルエチレンジアミン、1,2−シクロヘキサンジアミン、1,2−シクロヘプタンジアミン、2,3−ジメチルブタンジアミン、1−メチル−2,2−ジフェニルエチレンジアミン、1−イソブチル−2,2−ジフェニルエチレンジアミン、1−イソブロピル−2,2−ジフェニルエチレンジアミン、1−メチル−2,2−ジ(p−メトキシフェニル)エチレンジアミン、1−イソブチル−2,2−ジ(p−メトキシフェニル)エチレンジアミン、1−イソプロピル−2,2−ジ(p−メトキシフェニル)エチレンジアミン、1−ベンジル−2,2−ジ(p−メトキシフェニル)エチレンジアミン、1−メチル−2,2−ジナフチルエチレンジアミン、1−イソブチル−2,2−ジナフチルエチレンジアミン、1−イソプロピル−2,2−ジナフチルエチレンジアミン、2−メチルアミノ−1−フェニルエチルアミン、2−エチルアミノ−1−フェニルエチルアミン、2−n−プロピルアミノ−1−フェニルエチルアミン、2−i−プロピルアミノ−1−フェニルエチルアミン、2−n−ブチルアミノ−1−フェニルエチルアミン、2−tert−ブチルアミノ−1−フェニルエチルアミン、2−シクロヘキシルアミノ−1−フェニルエチルアミン、2−ベンジルアミノ−1−フェニルエチルアミン、2−ジメチルアミノ−1−フェニルエチルアミン、2−ジエチルアミノ−1−フェニルエチルアミン、2−ジn−プロピルアミノ−1−フェニルエチルアミン、2−ジi−プロピルアミノ−1−フェニルエチルアミン、2−ジn−ブチルアミノ−1−フェニルエチルアミン、2−ジtert−ブチルアミノ−1−フェニルエチルアミン、2−ピロリジニル−1−フェニルエチルアミン、2−ピペリジオ−1−フェニルエチルアミンなどの光学活性ジアミン化合物を例示することができる。
(i)Wは塩素原子、臭素原子又はヨウ素原子であり、Zはトリアルキルアミンであり、m=p=s=1、n=r=2、q=0を示し、(ii)Wは塩素原子、臭素原子又はヨウ素原子であり、Zはピリジル基又は環置換ピリジル基であり、m=n=r=s=1、p=2、q=0を示し、(iii)Wはアシルオキシ基であり、m=n=r=1、p=2、q=s=0を示し、(iv)Wは塩素原子、臭素原子又はヨウ素原子であり、Zはジメチルホルムアミド又はジメチルアセトアミドであり、m=n=r=1、p=2、q=0、sは0〜4の整数を示し、(v)Wは塩素原子、臭素原子又はヨウ素原子であり、Uは塩素原子、臭素原子又はヨウ素原子であり、Zはジアルキルアンモニウムイオンであり、m=n=p=2、q=3、r=s=1を示し、(vi)Wは塩素原子、臭素原子又はヨウ素原子であり、Uは中性配位子である芳香族化合物又はオレフィンであり、Zは塩素原子、臭素原子、ヨウ素原子、I3、BF4、ClO4、OTf、PF6、SbF6又はBPh4であり、m=n=p=q=r=s=1を示し、(vii)ZはBF4、ClO4、OTf、PF6、SbF6又はBPh4であり、m=n=r=1、p=q=0、s=2を示し、(viii)W及びUは同一であっても異なっていてもよく、水素原子、塩素原子、臭素原子、ヨウ素原子、カルボキシル基又は他のアニオン基であり、Zはジアミン化合物であり、m=n=p=q=r=s=1を示し、(ix)Wは水素原子であり、Uは塩素原子、臭素原子又はヨウ素原子であり、m=p=q=r=1、n=2、s=0を示し、(x)Wは水素原子であり、ZはBF4、ClO4、OTf、PF6、SbF6又はBPh4であり、m=n=p=r=s=1、q=0を示し、(xi)Wは塩素原子、臭素原子又はヨウ素原子であり、Uは一価ホスフィン配位子であり、Zは塩素原子、臭素原子又はヨウ素原子であり、m=n=p=q=1、r=z=2を示し、(xii)W及びUは同一又は異なって、塩素原子、臭素原子又はヨウ素原子であり、m=n=p=q=r=1、s=0を示す。)
で表される化合物が挙げられる。
また、文献(J.Chem.Soc.、Chem.Commun.、1208頁、1989年)に記載の方法に準じて、ビス[ジヨード(パラ−シメン)ルテニウム]([Ru(p−cymene)I2]2)と光学活性二座ホスフィン配位子とを有機溶媒中で加熱撹拌することにより調製することができる。更に、日本国特開平11−189600号公報に記載の方法に準じて、文献(J.Chem.Soc.、Chem.Commun.、992頁、1985年)の方法に従い得られるRu2Cl4(L)2NEt3とジアミン化合物とを有機溶媒中で反応せしめて合成することができる。
Ru(OAc)2(L)、Ru(OCOCF3)2(L)、Ru2Cl4(L)2NEt3、[RuCl2(L)(dmf)n]、RuHCl(L)、RuHBr(L)、RuHI(L)、[{RuCl(L)}2(μ−Cl)3][Me2NH2]、[{RuBr(L)}2(μ−Br)3][Me2NH2]、[{RuI(L)}2(μ−I)3][Me2NH2]、[{RuCl(L)}2(μ−Cl)3][Me2NH2]、[{RuBr(L)}2(μ−Br)3][Me2NH2]、[{RuBr(L)}2(μ−I)3][Me2NH2]、[RuCl[PPh3](L)]2(μ−Cl)2、[RuBr[PPh3](L)]2(μ−Br)2、[RuI[PPh3](L)]2(μ−I)2、RuCl2(L)、RuBr2(L)、RuI2(L)、[RuCl2(L)](dmf)n、RuCl2(L)(pyridine)2、RuBr2(L)(pyridine)2、RuI2(L)(pyridine)2、RuCl2(L)(2,2’−dipyridine)、RuBr2(L)(2,2’−dipyridine)、RuI2(L)(2,2’−dipyridine)、[RuCl(benzene)(L)]Cl、[RuBr(benzene)(L)]Br、[RuI(benzene)(L)]I、[RuCl(p−cymene)(L)]Cl、[RuBr(p−cymene)(L)]Br、[RuI(p−cymene)(L)]I、[RuI(p−cymene)(L)]I3、[Ru(L)](OTf)2、[Ru(L)](BF4)2、[Ru(L)](ClO4)2、[Ru(L)](SbF6)2、[Ru(L)](PF6)2、[Ru(L)](BPh4)2、[RuCl2(L)](en)、[RuBr2(L)](en)、[RuI2(L)](en)、[RuH2(L)](en)、[RuCl2(L)](DPEN)、[RuBr2(L)](DPEN)、[RuI2(L)](DPEN)、[RuH2(L)](DPEN)、[RuCl2(L)](DAIPEN)、[RuBr2(L)](DAIPEN)、[RuI2(L)](DAIPEN)、[RuH2(L)](DAIPEN)、[RuCl2(L)](MAE)、[RuBr2(L)](MAE)、[RuI2(L)](MAE)、[RuH2(L)](MAE)、[RuCl2(L)](EAE)、[RuBr2(L)](EAE)、[RuI2(L)](EAE)、[RuH2(L)](EAE)、[RuCl2(L)](MAPE)、[RuBr2(L)](MAPE)、[RuI2(L)](MAPE)、[RuH2(L)](MAPE)、[RuCl2(L)](DMAPE)、[RuBr2(L)](DMAPE)、[RuI2(L)](DMAPE)、[RuH2(L)](DMAPE)、[RuCl2(L)](DBAE)、[RuBr2(L)](DBAE)、[RuI2(L)](DBAE)、[RuH2(L)](DBAE)、[RuCl2(L)](DBAPE)、[RuBr2(L)](DBAPE)、[RuI2(L)](DBAPE)、[RuH2(L)](DBAPE)等を挙げることができる。
Ru2Cl4(L)2NEt3、[RuCl2(L)(dmf)n]、[{RuCl(L)}2(μ−Cl)3][Me2NH2]、[{RuBr(L)}2(μ−Br)3][Me2NH2]、[{RuI(L)}2(μ−I)3][Me2NH2]、[{RuCl(L)}2(μ−Cl)3][Me2NH2]、[{RuBr(L)}2(μ−Br)3][Me2NH2]、[{RuBr(L)}2(μ−I)3][Me2NH2]、[RuCl(benzene)(L)]Cl、[RuBr(benzene)(L)]Br、[RuI(benzene)(L)]I、[RuCl(p−cymene)(L)]Cl、[RuBr(p−cymene)(L)]Br、[RuI(p−cymene)(L)]I、[RuI(p−cymene)(L)]I3、[RuCl2(L)](MAE)、[RuBr2(L)](MAE)、[RuI2(L)](MAE)、[RuH2(L)](MAE)、[RuCl2(L)](EAE)、[RuBr2(L)](EAE)、[RuI2(L)](EAE)、[RuH2(L)](EAE)、[RuCl2(L)](MAPE)、[RuBr2(L)](MAPE)、[RuI2(L)](MAPE)、[RuH2(L)](MAPE)、[RuCl2(L)](DMAPE)、[RuBr2(L)](DMAPE)、[RuI2(L)](DMAPE)、[RuH2(L)](DMAPE)、[RuCl2(L)](DBAE)、[RuBr2(L)](DBAE)、[RuI2(L)](DBAE)、[RuH2(L)](DBAE)、[RuCl2(L)](DBAPE)、[RuBr2(L)](DBAPE)、[RuI2(L)](DBAPE)、[RuH2(L)](DBAPE)等を挙げることができる。
(式中、M’は、Li、Na又はKの金属を示し、Z’は、Cl、Br又はIのハロゲン原子を示す)
さらに、本発明では光学活性二座ホスフィン配位子と合わせて光学活性窒素化合物とを使用する。光学活性窒素化合物は、(S)−体及び(R)−体が存在するので、目的とする光学活性アルデヒド(1)の絶対配置に応じていずれかを選択すればよい。
すなわち、基質として、例えば、(E)−3−フェニル−4−メチル−2−ペンテノールを用いた場合、例えば、配位子としてTol−BINAPとDBAPEを用いたとき、(R)−体の光学活性3−フェニル−4−メチルペンタノールを得るには(S)−体のTol−BINAPと(R)−体のDBAPEを用い、(S)−体の光学活性3−フェニル−4−メチルペンタノールを得るには(R)−体のTol−BINAPと(S)−体のDBAPEを用いればよい。一方、基質として(Z)−体を用いた場合、(S)−体の光学活性3−フェニル−4−メチルペンタノールを得るには(R)−体のTol−BINAPと(S)−体のDBAPEを用い、(R)−体の光学活性3−フェニル−4−メチルペンタノールを得るには(S)−体のTol−BINAPと(R)−体のDBAPEを用いればよい。
また、添加する塩基の量は、遷移金属−光学活性ホスフィン錯体に対し、0.5〜100当量、好ましくは、2〜40当量であることが好ましい。
反応温度については、0〜150℃で行うことができるが、10〜70℃の範囲がより好ましい。また、反応時間は、反応基質濃度、温度等の反応条件によって異なるが、数分〜30時間で反応は完結する。反応終了後は、通常の後処理を行うことにより、目的とする光学活性アルデヒド(1)を単離することができる。
(E)−3−フェニル−4−メチル−2−ペンテノールの不斉異性化
1H NMR δ=0.77(d,J=6.7Hz,3H),0.95(d,J=6.7Hz,3H),1.26(br s,1H),1.87(m,1H),2.70−2.84(m,2H),2.88−3.00(m,1H),7.13−7.23(m,3H),7.25−7.32(m,2H).
実施例1において使用した触媒、基質と触媒のモル比、反応溶媒を表1に示したように変更した以外は、原料として(E)−3−フェニル−4−メチル−2−ペンテノールを用いて実施例1と同様の方法で反応を実施した。(3R)−3−フェニル−4−メチルペンタノールの収率は、実施例1と同様に、反応終了後、溶媒を減圧下濃縮し、残渣をガスクロマトグラフィー(カラム:SPELCO SLBTM−5ms)にて測定した。光学純度も実施例1と同様に、ガスクロマトグラフィー(カラム:Varian CHIRASIL−DEX CB)を用いて測定した。実施例1〜8、10及び参考例9の反応結果を表1に示す。
RuCl2[(R)−DBAPE][(S)−TolBINAP]
RuCl2[DBAE][(S)−TolBINAP]
触媒[D]:[RuCl{(S)−TolBINAP}(p−cymene)]Cl
触媒[E]:[(C2H5)2NH2][RuCl{(S)−TolBINAP}2(μ−Cl)3]
実施例1における基質と触媒のモル比、反応時間を表2に示したように変更し、表2に示した原料を用いた以外は、実施例1と同様の方法で反応を実施した。反応収率は、実施例1と同様に、反応終了後、溶媒を減圧下濃縮し、残渣をガスクロマトグラフィー(カラム:SPELCO SLBTM−5ms)にて測定した。光学純度も実施例1と同様に、ガスクロマトグラフィー(カラム:Varian CHIRASIL−DEX CB,化合物(k),化合物(l)についてのみSPELCO−DEXTM225)を用いて測定した。化合物cについてのみ、生成物のアルデヒドを常法(NaBH4,次にAcCl,ピリジン)によりアルコールまで還元、アセチル化したのち、同様な手法で光学純度を決定した。反応結果を表2に示す。
[(E)−3−フェニル−4−メチル−2−ペンテノール]
化合物(b):Ra=4−CH3C6H4,Rb=i−C3H7
[(E)−3−(4−メチルフェニル)−4−メチル−2−ペンテノール]
化合物(c):Ra=4−CH3OC6H4,Rb=i−C3H7
[(E)−3−(4−メトキシフェニル)−4−メチル−2−ペンテノール]
化合物(d):Ra=4−ClC6H4,Rb=i−C3H7
[(E)−3−(4−クロロフェニル)−4−メチル−2−ペンテノール]
化合物(e):Ra=C6H5,Rb=cyclo−C6H11
[(E)−3−フェニル−3−シクロヘキシル−2−プロペノール]
化合物(f):Ra=C6H5,Rb=C2H5
[(E)−3−フェニル−2−ペンテノール]
化合物(g):Ra=C6H5,Rb=CH3
[(E)−3−フェニル−2−ブテノール]
化合物(h):Ra=i−C3H7,Rb=C6H5
[(Z)−3−フェニル−4−メチル−2−ペンテノール]
化合物(i):Ra=CF3,Rb=C6H5
[(E)−3−トリフルオロメチル−3−フェニル−2−プロペノール]
化合物(j):Ra=cyclo−C6H11,Rb=CH3
[(E)−3−シクロヘキシル−2−ブテノール
化合物(k):Ra=(CH3)2C=CH(CH2)2,Rb=CH3
[ゲラニオール((E)−3,7−ジメチル−2,6−オキタジエン−1−オール)]
化合物(l):Ra=CH3,Rb=(CH3)2C=CH(CH2)2
[ネロール((Z)−3,7−ジメチル−2,6−オキタジエン−1−オール)]
化合物(m):Ra=n−C4H9,Rb=CH3
[(E)−3−メチル−2−ヘプテノール]
Claims (2)
- 式(1)
で表される光学活性アルデヒドの製造方法であって、
式(2)
で表されるアリルアルコールを、アルコール系溶媒中、ルテニウム錯体と塩基の存在下に不斉異性化し、
前記ルテニウム錯体が、下記一般式(3)
[Ru m L n W p U q ] r Z s (3)
(式(3)中、
Lは、光学活性ホスフィン配位子であり;Wは塩素原子、臭素原子又はヨウ素原子であり、Uは、水素原子、ハロゲン原子、アシルオキシ基、アリール基、ジエン、アニオン又はL以外の配位子であり;Zはジメチルホルムアミド又はジメチルアセトアミドであり;m=n=r=1、p=2、q=0、sは0〜4の整数を示す、
Lは、光学活性ホスフィン配位子であり;Wは塩素原子、臭素原子又はヨウ素原子であり、Uは塩素原子、臭素原子又はヨウ素原子であり;Zはジアルキルアンモニウムイオンであり;m=n=p=2、q=3、r=s=1を示す、又は、
Lは、光学活性ホスフィン配位子であり;W及びUは同一であっても異なっていてもよく、水素原子、塩素原子、臭素原子、ヨウ素原子、カルボキシル基又は他のアニオン基であり;Zはジアミン化合物であり;m=n=p=q=r=s=1を示す。]
で表されることを特徴とする、製造方法。 - 前記アルコール系溶媒が、メタノール又はエタノールであることを特徴とする請求項1に記載の製造方法。
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