JP2016523882A - キラルピロリジン類を使用するキラル4−クロマノン類の生成 - Google Patents
キラルピロリジン類を使用するキラル4−クロマノン類の生成 Download PDFInfo
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- JP2016523882A JP2016523882A JP2016522629A JP2016522629A JP2016523882A JP 2016523882 A JP2016523882 A JP 2016523882A JP 2016522629 A JP2016522629 A JP 2016522629A JP 2016522629 A JP2016522629 A JP 2016522629A JP 2016523882 A JP2016523882 A JP 2016523882A
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- MSTDXOZUKAQDRL-UHFFFAOYSA-N 4-Chromanone Chemical class C1=CC=C2C(=O)CCOC2=C1 MSTDXOZUKAQDRL-UHFFFAOYSA-N 0.000 title abstract description 5
- 150000003235 pyrrolidines Chemical class 0.000 title 1
- 150000001875 compounds Chemical class 0.000 claims abstract description 104
- 239000000203 mixture Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 17
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 14
- 125000001424 substituent group Chemical group 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 13
- 125000003118 aryl group Chemical group 0.000 claims description 13
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 125000001072 heteroaryl group Chemical group 0.000 claims description 10
- 150000002576 ketones Chemical class 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 125000003107 substituted aryl group Chemical group 0.000 claims description 5
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 11
- 238000003786 synthesis reaction Methods 0.000 abstract description 10
- VZWXIQHBIQLMPN-UHFFFAOYSA-N chromane Chemical group C1=CC=C2CCCOC2=C1 VZWXIQHBIQLMPN-UHFFFAOYSA-N 0.000 abstract description 6
- 230000000707 stereoselective effect Effects 0.000 abstract description 6
- 150000002148 esters Chemical class 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- 239000002253 acid Substances 0.000 description 11
- GVJHHUAWPYXKBD-UHFFFAOYSA-N (±)-α-Tocopherol Chemical compound OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 150000002009 diols Chemical class 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 125000002252 acyl group Chemical group 0.000 description 8
- LTUMRKDLVGQMJU-IUBLYSDUSA-N farnesyl acetone Chemical compound CC(C)=CCC\C(C)=C\CC\C(C)=C\CCC(C)=O LTUMRKDLVGQMJU-IUBLYSDUSA-N 0.000 description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 8
- 229940064063 alpha tocotrienol Drugs 0.000 description 7
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 239000011730 α-tocotrienol Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
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- RZFHLOLGZPDCHJ-DLQZEEBKSA-N alpha-Tocotrienol Natural products Oc1c(C)c(C)c2O[C@@](CC/C=C(/CC/C=C(\CC/C=C(\C)/C)/C)\C)(C)CCc2c1C RZFHLOLGZPDCHJ-DLQZEEBKSA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 150000007524 organic acids Chemical class 0.000 description 6
- WIGCFUFOHFEKBI-UHFFFAOYSA-N gamma-tocopherol Natural products CC(C)CCCC(C)CCCC(C)CCCC1CCC2C(C)C(O)C(C)C(C)C2O1 WIGCFUFOHFEKBI-UHFFFAOYSA-N 0.000 description 5
- 239000003223 protective agent Substances 0.000 description 5
- 239000011732 tocopherol Substances 0.000 description 5
- RZFHLOLGZPDCHJ-XZXLULOTSA-N α-Tocotrienol Chemical compound OC1=C(C)C(C)=C2O[C@@](CC/C=C(C)/CC/C=C(C)/CCC=C(C)C)(C)CCC2=C1C RZFHLOLGZPDCHJ-XZXLULOTSA-N 0.000 description 5
- 235000019145 α-tocotrienol Nutrition 0.000 description 5
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 4
- BTVWZWFKMIUSGS-UHFFFAOYSA-N 2-methylpropane-1,2-diol Chemical compound CC(C)(O)CO BTVWZWFKMIUSGS-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 4
- 229930003427 Vitamin E Natural products 0.000 description 4
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 description 4
- HNZUNIKWNYHEJJ-FMIVXFBMSA-N geranyl acetone Chemical compound CC(C)=CCC\C(C)=C\CCC(C)=O HNZUNIKWNYHEJJ-FMIVXFBMSA-N 0.000 description 4
- 150000007522 mineralic acids Chemical class 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 4
- 125000006239 protecting group Chemical class 0.000 description 4
- 229930003799 tocopherol Natural products 0.000 description 4
- 235000019165 vitamin E Nutrition 0.000 description 4
- 239000011709 vitamin E Substances 0.000 description 4
- 229940046009 vitamin E Drugs 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- GVJHHUAWPYXKBD-IEOSBIPESA-N α-tocopherol Chemical compound OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-IEOSBIPESA-N 0.000 description 4
- COFFUYZBRGBAQS-XFXZXTDPSA-N (z)-6,10-dimethylundec-5-en-2-one Chemical compound CC(C)CCC\C(C)=C/CCC(C)=O COFFUYZBRGBAQS-XFXZXTDPSA-N 0.000 description 3
- QPRQEDXDYOZYLA-UHFFFAOYSA-N 2-methylbutan-1-ol Chemical compound CCC(C)CO QPRQEDXDYOZYLA-UHFFFAOYSA-N 0.000 description 3
- GNBPEYCZELNJMS-UHFFFAOYSA-N 2-methylbutane-1,3-diol Chemical compound CC(O)C(C)CO GNBPEYCZELNJMS-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 150000001241 acetals Chemical class 0.000 description 3
- 150000001242 acetic acid derivatives Chemical class 0.000 description 3
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 3
- 238000004587 chromatography analysis Methods 0.000 description 3
- LTUMRKDLVGQMJU-UHFFFAOYSA-N famesylacetone Natural products CC(C)=CCCC(C)=CCCC(C)=CCCC(C)=O LTUMRKDLVGQMJU-UHFFFAOYSA-N 0.000 description 3
- WHWDWIHXSPCOKZ-UHFFFAOYSA-N hexahydrofarnesyl acetone Natural products CC(C)CCCC(C)CCCC(C)CCCC(C)=O WHWDWIHXSPCOKZ-UHFFFAOYSA-N 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 150000007519 polyprotic acids Polymers 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 150000003138 primary alcohols Chemical class 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 229960001295 tocopherol Drugs 0.000 description 3
- 229930003802 tocotrienol Natural products 0.000 description 3
- 239000011731 tocotrienol Substances 0.000 description 3
- 235000019148 tocotrienols Nutrition 0.000 description 3
- HUCXKZBETONXFO-NJFMWZAGSA-N (5e,9e,13e)-6,10,14,18-tetramethylnonadeca-5,9,13,17-tetraen-2-one Chemical compound CC(C)=CCC\C(C)=C\CC\C(C)=C\CC\C(C)=C\CCC(C)=O HUCXKZBETONXFO-NJFMWZAGSA-N 0.000 description 2
- YVYIAEXYJWDDJP-NJFMWZAGSA-N (5e,9e,13e)-6,10,14,18-tetramethylnonadeca-5,9,13-trien-2-one Chemical compound CC(C)CCC\C(C)=C\CC\C(C)=C\CC\C(C)=C\CCC(C)=O YVYIAEXYJWDDJP-NJFMWZAGSA-N 0.000 description 2
- CKJHJTOHWZLGFY-GHRIWEEISA-N (e)-6,10,14-trimethylpentadec-5-en-2-one Chemical compound CC(C)CCCC(C)CCC\C(C)=C\CCC(C)=O CKJHJTOHWZLGFY-GHRIWEEISA-N 0.000 description 2
- COFFUYZBRGBAQS-FMIVXFBMSA-N (e)-6,10-dimethylundec-5-en-2-one Chemical compound CC(C)CCC\C(C)=C\CCC(C)=O COFFUYZBRGBAQS-FMIVXFBMSA-N 0.000 description 2
- GJJVAFUKOBZPCB-ZGRPYONQSA-N (r)-3,4-dihydro-2-methyl-2-(4,8,12-trimethyl-3,7,11-tridecatrienyl)-2h-1-benzopyran-6-ol Chemical class OC1=CC=C2OC(CC/C=C(C)/CC/C=C(C)/CCC=C(C)C)(C)CCC2=C1 GJJVAFUKOBZPCB-ZGRPYONQSA-N 0.000 description 2
- CKJHJTOHWZLGFY-LGMDPLHJSA-N (z)-6,10,14-trimethylpentadec-5-en-2-one Chemical compound CC(C)CCCC(C)CCC\C(C)=C/CCC(C)=O CKJHJTOHWZLGFY-LGMDPLHJSA-N 0.000 description 2
- ADMGWHTWSYEIOQ-UHFFFAOYSA-N 1-(2,5-dihydroxy-3,4,6-trimethylphenyl)ethanone Chemical compound CC(=O)C1=C(C)C(O)=C(C)C(C)=C1O ADMGWHTWSYEIOQ-UHFFFAOYSA-N 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- PFNHSEQQEPMLNI-UHFFFAOYSA-N 2-methyl-1-pentanol Chemical compound CCCC(C)CO PFNHSEQQEPMLNI-UHFFFAOYSA-N 0.000 description 2
- OTXNTMVVOOBZCV-UHFFFAOYSA-N 2R-gamma-tocotrienol Natural products OC1=C(C)C(C)=C2OC(CCC=C(C)CCC=C(C)CCC=C(C)C)(C)CCC2=C1 OTXNTMVVOOBZCV-UHFFFAOYSA-N 0.000 description 2
- MXLMTQWGSQIYOW-UHFFFAOYSA-N 3-methyl-2-butanol Chemical compound CC(C)C(C)O MXLMTQWGSQIYOW-UHFFFAOYSA-N 0.000 description 2
- IWTBVKIGCDZRPL-UHFFFAOYSA-N 3-methylpentanol Chemical compound CCC(C)CCO IWTBVKIGCDZRPL-UHFFFAOYSA-N 0.000 description 2
- RBGLEUBCAJNCTR-UHFFFAOYSA-N 6,10-dimethylundecan-2-one Chemical compound CC(C)CCCC(C)CCCC(C)=O RBGLEUBCAJNCTR-UHFFFAOYSA-N 0.000 description 2
- OGZVHVGIGVSUEE-QUFKBVBHSA-N 6-hydroxy-2,5,7,8-tetramethyl-2-[(3e,7e)-4,8,12-trimethyltrideca-3,7,11-trienyl]-3h-chromen-4-one Chemical compound OC1=C(C)C(C)=C2OC(CC/C=C(C)/CC/C=C(C)/CCC=C(C)C)(C)CC(=O)C2=C1C OGZVHVGIGVSUEE-QUFKBVBHSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000004358 Butane-1, 3-diol Substances 0.000 description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004146 Propane-1,2-diol Substances 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 2
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- 229940087168 alpha tocopherol Drugs 0.000 description 2
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- 235000019437 butane-1,3-diol Nutrition 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- HNZUNIKWNYHEJJ-UHFFFAOYSA-N geranyl acetone Natural products CC(C)=CCCC(C)=CCCC(C)=O HNZUNIKWNYHEJJ-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 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 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
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 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
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- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- ZOCHHNOQQHDWHG-UHFFFAOYSA-N n-hexan-3-ol Natural products CCCC(O)CC ZOCHHNOQQHDWHG-UHFFFAOYSA-N 0.000 description 2
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- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- FQTLCLSUCSAZDY-UHFFFAOYSA-N nerolidol group Chemical group OC(C)(C=C)CCC=C(C)CCC=C(C)C FQTLCLSUCSAZDY-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 239000012044 organic layer Substances 0.000 description 2
- JYVLIDXNZAXMDK-UHFFFAOYSA-N pentan-2-ol Chemical compound CCCC(C)O JYVLIDXNZAXMDK-UHFFFAOYSA-N 0.000 description 2
- AQIXEPGDORPWBJ-UHFFFAOYSA-N pentan-3-ol Chemical compound CCC(O)CC AQIXEPGDORPWBJ-UHFFFAOYSA-N 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
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- 238000003756 stirring Methods 0.000 description 2
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- AOBORMOPSGHCAX-DGHZZKTQSA-N tocofersolan Chemical compound OCCOC(=O)CCC(=O)OC1=C(C)C(C)=C2O[C@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C AOBORMOPSGHCAX-DGHZZKTQSA-N 0.000 description 2
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- WGVKWNUPNGFDFJ-DQCZWYHMSA-N β-tocopherol Chemical compound OC1=CC(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C WGVKWNUPNGFDFJ-DQCZWYHMSA-N 0.000 description 2
- QUEDXNHFTDJVIY-UHFFFAOYSA-N γ-tocopherol Chemical class OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1 QUEDXNHFTDJVIY-UHFFFAOYSA-N 0.000 description 2
- GZIFEOYASATJEH-VHFRWLAGSA-N δ-tocopherol Chemical compound OC1=CC(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1 GZIFEOYASATJEH-VHFRWLAGSA-N 0.000 description 2
- 239000001618 (3R)-3-methylpentan-1-ol Substances 0.000 description 1
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- FOYKKGHVWRFIBD-UHFFFAOYSA-N gamma-tocopherol acetate Natural products CC(=O)OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1 FOYKKGHVWRFIBD-UHFFFAOYSA-N 0.000 description 1
- HNZUNIKWNYHEJJ-XFXZXTDPSA-N geranylacetone Chemical compound CC(C)=CCC\C(C)=C/CCC(C)=O HNZUNIKWNYHEJJ-XFXZXTDPSA-N 0.000 description 1
- HUCXKZBETONXFO-UHFFFAOYSA-N geranylnerylacetone Natural products CC(C)=CCCC(C)=CCCC(C)=CCCC(C)=CCCC(C)=O HUCXKZBETONXFO-UHFFFAOYSA-N 0.000 description 1
- QNVRIHYSUZMSGM-UHFFFAOYSA-N hexan-2-ol Chemical compound CCCCC(C)O QNVRIHYSUZMSGM-UHFFFAOYSA-N 0.000 description 1
- 150000002485 inorganic esters Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- NSPJNIDYTSSIIY-UHFFFAOYSA-N methoxy(methoxymethoxy)methane Chemical compound COCOCOC NSPJNIDYTSSIIY-UHFFFAOYSA-N 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- KPSSIOMAKSHJJG-UHFFFAOYSA-N neopentyl alcohol Chemical compound CC(C)(C)CO KPSSIOMAKSHJJG-UHFFFAOYSA-N 0.000 description 1
- WASNIKZYIWZQIP-AWEZNQCLSA-N nerolidol Natural products CC(=CCCC(=CCC[C@@H](O)C=C)C)C WASNIKZYIWZQIP-AWEZNQCLSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000002905 orthoesters Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- ALBOWYHOENOWIO-UHFFFAOYSA-N pentadeca-5,9,13-trien-2-one Chemical compound CC=CCCC=CCCC=CCCC(C)=O ALBOWYHOENOWIO-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- -1 phosphate ester Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- BOTWFXYSPFMFNR-PYDDKJGSSA-N phytol Chemical compound CC(C)CCC[C@@H](C)CCC[C@@H](C)CCC\C(C)=C\CO BOTWFXYSPFMFNR-PYDDKJGSSA-N 0.000 description 1
- DFOXKPDFWGNLJU-UHFFFAOYSA-N pinacolyl alcohol Chemical compound CC(O)C(C)(C)C DFOXKPDFWGNLJU-UHFFFAOYSA-N 0.000 description 1
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000013074 reference sample Substances 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003900 succinic acid esters Chemical class 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 150000003611 tocopherol derivatives Chemical class 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 235000007680 β-tocopherol Nutrition 0.000 description 1
- 239000011590 β-tocopherol Substances 0.000 description 1
- 235000019151 β-tocotrienol Nutrition 0.000 description 1
- 239000011723 β-tocotrienol Substances 0.000 description 1
- FGYKUFVNYVMTAM-WAZJVIJMSA-N β-tocotrienol Chemical compound OC1=CC(C)=C2O[C@@](CC/C=C(C)/CC/C=C(C)/CCC=C(C)C)(C)CCC2=C1C FGYKUFVNYVMTAM-WAZJVIJMSA-N 0.000 description 1
- 239000002478 γ-tocopherol Substances 0.000 description 1
- QUEDXNHFTDJVIY-DQCZWYHMSA-N γ-tocopherol Chemical compound OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1 QUEDXNHFTDJVIY-DQCZWYHMSA-N 0.000 description 1
- 235000019150 γ-tocotrienol Nutrition 0.000 description 1
- 239000011722 γ-tocotrienol Substances 0.000 description 1
- OTXNTMVVOOBZCV-WAZJVIJMSA-N γ-tocotrienol Chemical compound OC1=C(C)C(C)=C2O[C@@](CC/C=C(C)/CC/C=C(C)/CCC=C(C)C)(C)CCC2=C1 OTXNTMVVOOBZCV-WAZJVIJMSA-N 0.000 description 1
- 239000002446 δ-tocopherol Substances 0.000 description 1
- 235000019144 δ-tocotrienol Nutrition 0.000 description 1
- 239000011729 δ-tocotrienol Substances 0.000 description 1
- ODADKLYLWWCHNB-LDYBVBFYSA-N δ-tocotrienol Chemical compound OC1=CC(C)=C2O[C@@](CC/C=C(C)/CC/C=C(C)/CCC=C(C)C)(C)CCC2=C1 ODADKLYLWWCHNB-LDYBVBFYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
- C07D311/22—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Pyrane Compounds (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
本発明は、トコフェロールおよびトコトリエノールの合成の分野に関する。
クロマン化合物は、キラル天然物および生物活性化合物の重要なクラスを代表する。クロマン化合物の1つの重要なクラスは、ビタミンEおよびそのエステルである。多くの場合、ビタミンEは、そのエステルの形態で商品化されており、なぜなら後者は向上した安定性を示すからである。
したがって、本発明が解決しようとする課題は、クロマノン環またはクロマン環における2位から考えて立体特異的な状態でのクロマノン類またはクロマン類(すなわち、式(I)または(V)の化合物)の合成のための方法を提供することである。
第1の態様において、本発明は、式(I)
の化合物の製造方法であって、
− 式(II−A)の化合物
− 式(II−B)の化合物またはそのケタール、および
− 少なくとも1種の式(II−C)のキラル化合物
からなる組成物を反応させる工程を含み、
式中、R1、R3およびR4は、互いに独立して、水素またはメチル基であり、
R2およびR2’は、水素またはフェノール保護基を表し、
R5は、直鎖もしくは分岐の完全に飽和したC6〜25アルキル基または少なくとも1個の炭素−炭素二重結合を含む直鎖もしくは分岐のC6〜25アルキル基のいずれかを表し、
Y1は、CH2Y2または
[式中、R6は、少なくとも1個の芳香族基および/またはC=Oおよび/またはNHおよび/またはNH2基を任意選択でさらに含む直鎖または分岐のC1〜12アルキル基を表し、
Y2は、OHまたはOR7またはNHR7またはNHCOOR7または
(式中、R7は、
少なくとも1個の芳香族基および/もしくはC=Oおよび/もしくはNHおよび/もしくはNH2基を任意選択でさらに含む直鎖もしくは分岐のC1〜12アルキル基、
または
アリール基もしくは置換アリール基もしくはヘテロアリール基もしくは置換ヘテロアリール基
のいずれかを表す)のいずれかを表し、および
点線は、対応する置換基を式(II−C)の残部に結合している結合を表す]のいずれかを表し、
式中、*は、式(I)のキラル異性体のキラル中心を表す、
方法に関する。
R1=R3=R4=CH3
または
R1=R4=CH3、R3=H
または
R1=H、R3=R4=CH3
または
R1=R3=H、R4=CH3
である。
である。
・α−トコフェロール(R1=R3=R4=CH3、R5=(II−A)、特に(II−ARR)、R2=H)、
・β−トコフェロール(R1=R4=CH3、R3=H、R5=(II−A)、特に(II−ARR)、R2=H)、
・γ−トコフェロール(R1=H、R3=R4=CH3、R5=(II−A)、特に(II−ARR)、R2=H)、
・δ−トコフェロール(R1=R3=H、R4=CH3、R5=(II−A)、特に(II−ARR)、R2=H)、
・α−トコトリエノール(R1=R3=R4=CH3、R5=(II−B)、R2=H)、
・β−トコトリエノール(R1=R4=CH3、R3=H、R5=(II−B)、R2=H)、
・γ−トコトリエノール(R1=H、R3=R4=CH3、R5=(II−B)、R2=H)、
・δ−トコトリエノール(R1=R3=H、R4=CH3、R5=(II−B)、R2=H)、
およびそれらのエステル、特に、酢酸エステル(R2=COCH3)、またはリン酸エステル
からなる群から選択される異性体である。
a)少なくとも1種の式(II−A)の化合物、および
b)少なくとも1種の式(II−B)のケトンまたはそのケタール、および
c)少なくとも1種の式(II−C)のキラル化合物
からなる組成物に関する。
本発明を、以下の実験によりさらに説明する。
0.5mmol(100mgに相当)の2−アセチル−3,5,6−トリメチルヒドロキノンを、磁気撹拌棒、加熱デバイス、水分離器およびアルゴン供給源を備えた20mL丸底フラスコ中に、23℃で添加した。次いで、0.514mmol(134mgに相当)のE,E−ファルネシルアセトンを添加し、実施例1については、最後に0.795mmolの表1に示す塩基を添加した。実施例対照3の場合は、E,E−ファルネシルアセトンを添加する前に、2.5mL(2.2gに相当)のトルエンをフラスコ中に添加した。
1H NMR(CDCl3,300MHz)δ1.30(s,3H);1.51(s,6H);1.52(s,3H);1.54−1.58(m,1H);1.61(d,J=0.9Hz,3H);1.67−1.78(m,1H);1.67−2.10(m,10H);2.08(s,3H);2.16(s,3H);2.48(s,3H);2.51(d,J=15.8Hz,1H);2.68(d,J=15.8Hz,1H),4.45(s br,1H);4.99−5.05(m,3H)ppm.
13C NMR(CDCl3,75.5MHz)δ12.1;12.8;13.3;15.9;16.0;17.7;22.2;23.7;25.1;26.6;26.8;39.4;39.7(2C);49.5;79.4;116.7;120.4;123.5;124.0;124.1;124.4;131.3;132.0;135.1;135.7;145.8;152.8;195.2ppm.
6−ヒドロキシ−2,5,7,8−テトラメチル−2−((3E,7E)−4,8,12−トリメチルトリデカ−3,7,11−トリエン−1−イル)クロマン−4−オンを、Baldenius et al.(欧州特許出願公開第0989126A1号明細書)により詳細に記載されているように、亜鉛末および塩酸水での処理により、α−トコトリエノールに変換した。
Claims (9)
- 式(I)
の化合物の製造方法であって、
− 式(II−A)の化合物、
− 式(II−B)の化合物またはそのケタール、および
− 少なくとも1種の式(II−C)のキラル化合物
からなる組成物を反応させる工程を含み、
式中、R1、R3およびR4は、互いに独立して、水素またはメチル基であり、
R2およびR2’は、水素またはフェノール保護基を表し、
R5は、直鎖もしくは分岐の完全に飽和したC6〜25アルキル基または少なくとも1個の炭素−炭素二重結合を含む直鎖もしくは分岐のC6〜25アルキル基のいずれかを表し、
Y1は、CH2Y2または
[式中、R6は、少なくとも1個の芳香族基および/またはC=Oおよび/またはNHおよび/またはNH2基を任意選択でさらに含む直鎖または分岐のC1〜12アルキル基を表し、
Y2は、OHまたはOR7またはNHR7またはNHCOOR7または
(式中、R7は、
少なくとも1個の芳香族基および/もしくはC=Oおよび/もしくはNHおよび/もしくはNH2基を任意選択でさらに含む直鎖もしくは分岐のC1〜12アルキル基、
または
アリール基もしくは置換アリール基もしくはヘテロアリール基もしくは置換ヘテロアリール基
のいずれかを表す)のいずれかを表し、および
点線は、前記対応する置換基を式(II−C)の残部に結合している結合を表す]のいずれかを表し、
式中、*は、式(I)のキラル異性体のキラル中心を表す、
方法。 - R1=R3=R4=CH3
または
R1=R4=CH3、R3=H
または
R1=H、R3=R4=CH3
または
R1=R3=H、R4=CH3
を特徴とする、請求項1または2に記載の方法。 - 式(I)または(V)中の*の付いた前記キラル中心においてR配置を有する異性体が、前記キラル中心においてS配置を有する対応する異性体と比較して選択的に生成されることを特徴とする、請求項1〜5のいずれか一項に記載の方法。
- a)少なくとも1種の式(II−A)の化合物、および
b)少なくとも1種の式(II−B)のケトンまたはそのケタール、および
c)少なくとも1種の式(II−C)のキラル化合物
からなる組成物であって、
式中、R1、R3およびR4は、互いに独立して、水素またはメチル基であり、
R2’は、水素またはフェノール保護基を表し、
R5は、直鎖もしくは分岐の完全に飽和したC6〜25アルキル基または少なくとも1個の炭素−炭素二重結合を含む直鎖もしくは分岐のC6〜25アルキル基のいずれかを表し、
Y1は、CH2Y2または
[式中、R6は、少なくとも1個の芳香族基および/またはC=Oおよび/またはNHおよび/またはNH2基を任意選択でさらに含む直鎖または分岐のC1〜12アルキル基を表し、
Y2は、OHまたはOR7またはNHR7またはNHCOOR7または
(式中、R7は、
少なくとも1個の芳香族基および/もしくはC=Oおよび/もしくはNHおよび/もしくはNH2基を任意選択でさらに含む直鎖もしくは分岐のC1〜12アルキル基、
または
アリール基もしくは置換アリール基もしくはヘテロアリール基もしくは置換ヘテロアリール基
のいずれかを表す)のいずれかを表し、および
点線は、前記対応する置換基を式(II−C)の残部に結合している結合を表す]のいずれかを表す、
組成物。
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EP13175317.0 | 2013-07-05 | ||
PCT/EP2014/064210 WO2015001031A1 (en) | 2013-07-05 | 2014-07-03 | Formation of chiral 4-chromanones using chiral pyrrolidines |
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EP (1) | EP3016942B1 (ja) |
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Citations (1)
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JPS5219670A (en) * | 1975-08-07 | 1977-02-15 | Bayer Ag | Chromann44ons and preparation method thereof |
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DE19843672A1 (de) | 1998-09-23 | 2000-03-30 | Basf Ag | Verfahren zur Herstellung von Chromanol-Derivaten |
ATE520678T1 (de) | 2004-12-22 | 2011-09-15 | Dsm Ip Assets Bv | Asymmetrische hydrierung von alkenen mit chiralem iridiumkomplex |
CN101778810A (zh) | 2007-08-08 | 2010-07-14 | 帝斯曼知识产权资产管理有限公司 | (e,e)-法尼基丙酮的制备方法 |
EP2522647B1 (en) | 2011-05-10 | 2014-04-30 | DSM IP Assets B.V. | Process of separating chiral isomers of chroman compounds and their derivatives and precursors |
-
2014
- 2014-07-03 US US14/902,873 patent/US20160152588A1/en not_active Abandoned
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Publication number | Priority date | Publication date | Assignee | Title |
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JPS5219670A (en) * | 1975-08-07 | 1977-02-15 | Bayer Ag | Chromann44ons and preparation method thereof |
Non-Patent Citations (2)
Title |
---|
CARPENTER, R. D. ET AL, ANGEW. CHEM. INT. ED., vol. vol.47, JPN6018001385, 2008, pages 6407 - 6410 * |
KABBE, H-J. ET AL., ANGEW. CHEM. INT. ED. ENGL, vol. vol.21, JPN6018001384, 1982, pages 247 - 256 * |
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CN105358542B (zh) | 2017-10-24 |
JP6365949B2 (ja) | 2018-08-01 |
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