JP4696274B2 - 固体キラルジルコニウム触媒及びそれを用いたアルドール反応物又は環化体化合物の合成方法 - Google Patents
固体キラルジルコニウム触媒及びそれを用いたアルドール反応物又は環化体化合物の合成方法 Download PDFInfo
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- JP4696274B2 JP4696274B2 JP2007051428A JP2007051428A JP4696274B2 JP 4696274 B2 JP4696274 B2 JP 4696274B2 JP 2007051428 A JP2007051428 A JP 2007051428A JP 2007051428 A JP2007051428 A JP 2007051428A JP 4696274 B2 JP4696274 B2 JP 4696274B2
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- 239000003054 catalyst Substances 0.000 title claims description 38
- 229910052726 zirconium Inorganic materials 0.000 title claims description 35
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 title claims description 34
- 239000007787 solid Substances 0.000 title claims description 31
- 150000001875 compounds Chemical class 0.000 title claims description 28
- HSJKGGMUJITCBW-UHFFFAOYSA-N 3-hydroxybutanal Chemical compound CC(O)CC=O HSJKGGMUJITCBW-UHFFFAOYSA-N 0.000 title claims description 20
- 239000000376 reactant Substances 0.000 title claims description 11
- 238000000034 method Methods 0.000 title claims description 9
- 230000002194 synthesizing effect Effects 0.000 title claims description 7
- -1 aldehyde compound Chemical class 0.000 claims description 55
- 238000003786 synthesis reaction Methods 0.000 claims description 40
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 230000015572 biosynthetic process Effects 0.000 claims description 23
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 9
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 239000010703 silicon Substances 0.000 claims description 9
- 150000003755 zirconium compounds Chemical class 0.000 claims description 9
- 239000002244 precipitate Substances 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 239000012454 non-polar solvent Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 4
- 229910052740 iodine Inorganic materials 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 65
- 238000005481 NMR spectroscopy Methods 0.000 description 37
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 30
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 27
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 21
- 238000004128 high performance liquid chromatography Methods 0.000 description 20
- BHIWKHZACMWKOJ-UHFFFAOYSA-N methyl isobutyrate Chemical compound COC(=O)C(C)C BHIWKHZACMWKOJ-UHFFFAOYSA-N 0.000 description 20
- 239000000047 product Substances 0.000 description 20
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 19
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 18
- 239000000126 substance Substances 0.000 description 17
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 15
- 238000005575 aldol reaction Methods 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- 238000006077 hetero Diels-Alder cycloaddition reaction Methods 0.000 description 11
- 230000003197 catalytic effect Effects 0.000 description 10
- WDAXFOBOLVPGLV-UHFFFAOYSA-N isobutyric acid ethyl ester Natural products CCOC(=O)C(C)C WDAXFOBOLVPGLV-UHFFFAOYSA-N 0.000 description 10
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 8
- 150000002430 hydrocarbons Chemical group 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 230000007774 longterm Effects 0.000 description 7
- 238000003860 storage Methods 0.000 description 7
- LRDIEHDJWYRVPT-UHFFFAOYSA-N 4-amino-5-hydroxynaphthalene-1-sulfonic acid Chemical compound C1=CC(O)=C2C(N)=CC=C(S(O)(=O)=O)C2=C1 LRDIEHDJWYRVPT-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- DYUMLJSJISTVPV-UHFFFAOYSA-N phenyl propanoate Chemical compound CCC(=O)OC1=CC=CC=C1 DYUMLJSJISTVPV-UHFFFAOYSA-N 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- YGCZTXZTJXYWCO-UHFFFAOYSA-N 3-phenylpropanal Chemical compound O=CCCC1=CC=CC=C1 YGCZTXZTJXYWCO-UHFFFAOYSA-N 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 4
- 230000021736 acetylation Effects 0.000 description 4
- 238000006640 acetylation reaction Methods 0.000 description 4
- 125000000623 heterocyclic group Chemical group 0.000 description 4
- JARKCYVAAOWBJS-UHFFFAOYSA-N hexanal Chemical compound CCCCCC=O JARKCYVAAOWBJS-UHFFFAOYSA-N 0.000 description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- KJPRLNWUNMBNBZ-QPJJXVBHSA-N (E)-cinnamaldehyde Chemical compound O=C\C=C\C1=CC=CC=C1 KJPRLNWUNMBNBZ-QPJJXVBHSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- 239000012300 argon atmosphere Substances 0.000 description 3
- 229940117916 cinnamic aldehyde Drugs 0.000 description 3
- KJPRLNWUNMBNBZ-UHFFFAOYSA-N cinnamic aldehyde Natural products O=CC=CC1=CC=CC=C1 KJPRLNWUNMBNBZ-UHFFFAOYSA-N 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 239000011949 solid catalyst Substances 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- AXMVYSVVTMKQSL-UHFFFAOYSA-N UNPD142122 Natural products OC1=CC=C(C=CC=O)C=C1O AXMVYSVVTMKQSL-UHFFFAOYSA-N 0.000 description 2
- 238000011914 asymmetric synthesis Methods 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000007809 chemical reaction catalyst Substances 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- SHALBPKEGDBVKK-VOTSOKGWSA-N danishefsky's diene Chemical class CO\C=C\C(=C)O[Si](C)(C)C SHALBPKEGDBVKK-VOTSOKGWSA-N 0.000 description 2
- 239000011982 enantioselective catalyst Substances 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- ZRSNZINYAWTAHE-UHFFFAOYSA-N p-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C=C1 ZRSNZINYAWTAHE-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000004809 thin layer chromatography Methods 0.000 description 2
- FZAHUWLRLKATJP-ZDUSSCGKSA-N (2R)-2-(2-phenylethenyl)-2,3-dihydropyran-4-one Chemical compound O1C=CC(=O)C[C@@H]1C=CC1=CC=CC=C1 FZAHUWLRLKATJP-ZDUSSCGKSA-N 0.000 description 1
- QMGYTHOMODNQTR-LLVKDONJSA-N (2r)-2-phenyl-2,3-dihydropyran-4-one Chemical compound O1C=CC(=O)C[C@@H]1C1=CC=CC=C1 QMGYTHOMODNQTR-LLVKDONJSA-N 0.000 description 1
- RKVXYIFLNONBNH-ZDUSSCGKSA-N (2s)-2-(2-phenylethyl)-2,3-dihydropyran-4-one Chemical compound O1C=CC(=O)C[C@@H]1CCC1=CC=CC=C1 RKVXYIFLNONBNH-ZDUSSCGKSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- YJGHLPFFDKDTOU-UHFFFAOYSA-N 2-(4-methylphenyl)-2,3-dihydropyran-4-one Chemical compound C1=CC(C)=CC=C1C1OC=CC(=O)C1 YJGHLPFFDKDTOU-UHFFFAOYSA-N 0.000 description 1
- FPYUJUBAXZAQNL-UHFFFAOYSA-N 2-chlorobenzaldehyde Chemical compound ClC1=CC=CC=C1C=O FPYUJUBAXZAQNL-UHFFFAOYSA-N 0.000 description 1
- QIWXWAKHFMFSBO-UHFFFAOYSA-N 2-pentyl-2,3-dihydropyran-4-one Chemical compound CCCCCC1CC(=O)C=CO1 QIWXWAKHFMFSBO-UHFFFAOYSA-N 0.000 description 1
- AVPYQKSLYISFPO-UHFFFAOYSA-N 4-chlorobenzaldehyde Chemical compound ClC1=CC=C(C=O)C=C1 AVPYQKSLYISFPO-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- DUCJVFKERFSSDX-UHFFFAOYSA-N CC(C(CCC1=CC=CC=C1)O)C(=O)OC2=CC=CC=C2 Chemical compound CC(C(CCC1=CC=CC=C1)O)C(=O)OC2=CC=CC=C2 DUCJVFKERFSSDX-UHFFFAOYSA-N 0.000 description 1
- YCIQVZDYOPECFW-NSHDSACASA-N CC(C)([C@H](c(cc1)ccc1OC)O)C(OC)=O Chemical compound CC(C)([C@H](c(cc1)ccc1OC)O)C(OC)=O YCIQVZDYOPECFW-NSHDSACASA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- XOVWOLBJLVKYIK-XVNBXDOJSA-N OC(C(C(=O)OC1=CC=CC=C1)C)\C=C\C Chemical compound OC(C(C(=O)OC1=CC=CC=C1)C)\C=C\C XOVWOLBJLVKYIK-XVNBXDOJSA-N 0.000 description 1
- BNCKMKFTEDZASH-OUKQBFOZSA-N OC(C(C(=O)OC1=CC=CC=C1)C)\C=C\C1=CC=CC=C1 Chemical compound OC(C(C(=O)OC1=CC=CC=C1)C)\C=C\C1=CC=CC=C1 BNCKMKFTEDZASH-OUKQBFOZSA-N 0.000 description 1
- ZVQOOHYFBIDMTQ-UHFFFAOYSA-N [methyl(oxido){1-[6-(trifluoromethyl)pyridin-3-yl]ethyl}-lambda(6)-sulfanylidene]cyanamide Chemical compound N#CN=S(C)(=O)C(C)C1=CC=C(C(F)(F)F)N=C1 ZVQOOHYFBIDMTQ-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000006480 benzoylation reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 description 1
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Natural products CC=CC=O MLUCVPSAIODCQM-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- FEXPAJSNUASWDX-JTQLQIEISA-N methyl (3S)-3-hydroxy-2,2-dimethyl-3-phenylpropanoate Chemical compound COC(=O)C(C)(C)[C@@H](O)C1=CC=CC=C1 FEXPAJSNUASWDX-JTQLQIEISA-N 0.000 description 1
- LOTIFVYNXBIRHU-MDZDMXLPSA-N methyl (e)-3-hydroxy-2,2-dimethyl-5-phenylpent-4-enoate Chemical compound COC(=O)C(C)(C)C(O)\C=C\C1=CC=CC=C1 LOTIFVYNXBIRHU-MDZDMXLPSA-N 0.000 description 1
- JSALHIFCZIJDKC-AATRIKPKSA-N methyl (e)-3-hydroxy-2,2-dimethylhex-4-enoate Chemical compound COC(=O)C(C)(C)C(O)\C=C\C JSALHIFCZIJDKC-AATRIKPKSA-N 0.000 description 1
- YCIQVZDYOPECFW-UHFFFAOYSA-N methyl 3-hydroxy-3-(4-methoxyphenyl)-2,2-dimethylpropanoate Chemical compound COC(=O)C(C)(C)C(O)C1=CC=C(OC)C=C1 YCIQVZDYOPECFW-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- FXLOVSHXALFLKQ-UHFFFAOYSA-N p-tolualdehyde Chemical compound CC1=CC=C(C=O)C=C1 FXLOVSHXALFLKQ-UHFFFAOYSA-N 0.000 description 1
- IZRCYFDORVIRRW-SWLSCSKDSA-N phenyl (2S,3R)-3-hydroxy-2-methyl-3-phenylpropanoate Chemical compound C1([C@H](O)[C@H](C)C(=O)OC=2C=CC=CC=2)=CC=CC=C1 IZRCYFDORVIRRW-SWLSCSKDSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical group C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- HZXJVDYQRYYYOR-UHFFFAOYSA-K scandium(iii) trifluoromethanesulfonate Chemical compound [Sc+3].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F HZXJVDYQRYYYOR-UHFFFAOYSA-K 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Pyrane Compounds (AREA)
Description
又、上記したアルデヒド化合物とダニシェフスキージエン化合物を反応させることにより、式(VIII)
量は、好ましくは3〜30モル%、より好ましくは5〜20モル%とする。また、ジルコニウム化合物の量は、好ましくは1〜30モル%、より好ましくは3〜15モル%とする。そして、このような割合となるよう、固体触媒作成時の式Iとジルコニウムの配合割合を調整する。反応時の固体キラルジルコニウム触媒としての使用量は、好ましくは1〜30モル%、より好ましくは3〜15モル%である(ジルコニウムベースとして)。 又、反応原料としてのジエン化合物に対し、アルデヒド化合物を、0.2〜2倍モル、より好適には0.5〜1.5倍モル程度とすることができる。 上記不斉アルドール反応、又は不斉ヘテロディールス−アルダー反応は溶媒中で行うことが好ましく、より好適には、炭化水素溶媒やハロゲン化炭化水素溶媒等を用いる。反応温度は、-20度〜30度、より好ましくは、-10度〜10度程度の範囲で行うことができ、反応の雰囲気は、不活性雰囲気が好ましい。
13C NMR (CDCl3) Anti isomer δ 14.3, 47.4, 76.3, 121.4, 125.8, 126.6, 128.1, 128.5, 129.3, 141.3, 150.5, 174.3; detectable peaks of Syn isomerδ 11.6, 46.9, 74.2, 121.3, 126.2, 127.7, 128.3, 173.8. HPLC (after acetylation); Daicel Chiralcel AS, hexane/iPrOH = 200/1, flow rate = 1.0 mL/min: Syn isomer tR = 13.3 min (major, 2R, 3R), tR = 22.0 min (minor, 2S, 3S); Anti isomer tR = 15.8 min (minor, 2R, 3S), tR = 30.7 min (major, 2S, 3R).
イソ酪酸メチル由来のケテンシリルアセタールの代わりにプロピオン酸フェニル由来のケテンシリルアセタールを使用し、ベンズアルデヒドの代わりにp−メトキシベンズアルデヒドを加えたこと以外は実施例2とまったく同様にして合成反応を行った。
得られた目的物(収率84%、syn/anti=6/94、97% ee (anti))の化学構造を式XVIIIに示す。
ベンズアルデヒドの代わりにp−クロロベンズアルデヒドを加えたこと以外は実施例15とまったく同様にして合成反応を行った。
得られた目的物(収率90%、81% ee)の化学構造を式XXIIIに示す。
24.9, 126.7, 128.5, 133.8, 135.6, 162.9, 191.8. HPLC; Daicel Chiralcel OD, hexane/iPrOH = 9/1, flow rate = 1.0 mL/min : tR = 21.1 min (S), tR =47.6 min (R).
Claims (3)
- 請求項1に記載の固体キラルジルコニウム触媒の存在下、アルデヒド化合物とケイ素エノラートとを反応させ、又はアルデヒド化合物とダニシェフスキージエン化合物とを反応させ、アルドール反応物又は環化体化合物を合成する方法。
- さらに、反応の際に一級アルコール化合物及び/又は水を添加する請求項2記載のアルドール反応物又は環化体化合物の合成方法。
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JP2007051428A JP4696274B2 (ja) | 2007-03-01 | 2007-03-01 | 固体キラルジルコニウム触媒及びそれを用いたアルドール反応物又は環化体化合物の合成方法 |
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JP2002356454A (ja) * | 2001-03-15 | 2002-12-13 | Japan Science & Technology Corp | ビナフトール誘導体とキラルジルコニウム触媒並びに不斉ヘテロデイールズ・アルダー反応方法 |
WO2003076072A1 (fr) * | 2002-03-11 | 2003-09-18 | Japan Science And Technology Agency | Catalyseur de zirconium chiral pratique |
JP2003299962A (ja) * | 2002-04-09 | 2003-10-21 | Japan Science & Technology Corp | キラルジルコニウム触媒とアンチ選択性非対称アルドール反応方法 |
JP2006022046A (ja) * | 2004-07-08 | 2006-01-26 | Japan Science & Technology Agency | 光学活性なβ−ヒドロキシ−α−アミノ酸誘導体の製造方法 |
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WO2003076072A1 (fr) * | 2002-03-11 | 2003-09-18 | Japan Science And Technology Agency | Catalyseur de zirconium chiral pratique |
JP2003299962A (ja) * | 2002-04-09 | 2003-10-21 | Japan Science & Technology Corp | キラルジルコニウム触媒とアンチ選択性非対称アルドール反応方法 |
JP2006022046A (ja) * | 2004-07-08 | 2006-01-26 | Japan Science & Technology Agency | 光学活性なβ−ヒドロキシ−α−アミノ酸誘導体の製造方法 |
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