| Project/Area Number |
07457520
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| Research Category |
Grant-in-Aid for Scientific Research (B)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
Chemical pharmacy
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| Research Institution | KYOTO UNIVERSITY (1996-1997)
Osaka University (1995) |
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Principal Investigator |
TOMIOKA Kiyoshi KYOTO UNIVERSITY Gradate School of Pharmaceutical Sciences, Professor, 薬学研究科, 教授 (50114575)
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| Co-Investigator(Kenkyū-buntansha) |
NAGAOKA Yasuo KYOTO UNIVERSITY,Gradate School of Pharmaceutical Sciences, Instructor, 薬学研究科, 助手 (90243039)
IIDA Akira KYOTO UNIVERSITY,Gradate School of Pharmaceutical Sciences, Associate Professor, 薬学研究科, 助教授 (40202816)
市原 潤子 大阪大学, 産業科学研究所, 助手 (60110772)
金井 求 大阪大学, 産業科学研究所, 助手 (20243264)
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| Project Period (FY) |
1995 – 1997
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| Project Status |
Completed (Fiscal Year 1997)
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| Budget Amount *help |
¥7,600,000 (Direct Cost: ¥7,600,000)
Fiscal Year 1997: ¥2,100,000 (Direct Cost: ¥2,100,000)
Fiscal Year 1996: ¥1,900,000 (Direct Cost: ¥1,900,000)
Fiscal Year 1995: ¥3,600,000 (Direct Cost: ¥3,600,000)
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| Keywords | enantioselective reaction / conjugate addition / imine / lithium enolate / LUMO coefficients / ligand / catalytic reaction / beta-lactam / 有機銅 / 錯体 / ホスフィン / 立体選択性 / 配座変換 / 反応面 / 求核付加反応 / 不斉補助剤 |
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| Research Abstract |
We have reported the successful chiral ligand-mediated asymmetric 1,2- and 1,4-addition reactions of organolithiums to various imines of aryl and alpha, beta-unsaturated aldehydes Thus, organo-lithiums add to the cyclohexylimines 1,2 (R=c-C6Hll) in 1,4-fashion to give, after hydrolysis, the corresponding aldehydes in up to 99% ee and in high to good yields. On the other hand, the reactions with arylimines exclusively afford 1,2-adducts in up to 90% ee and in nearly quantitative yields, giving us a good method for the preparation of chiral amines. It is also interesting in that the reactions with both cyclohexyl- and arylimines of 1-fluoronaphthalene-2-carbaldehyde exclusively proceed in 1,4-fashion to provide nucleophilic aromatic substitution products in high yields. Since deep understanding of the factors governing regioselectivity is a long-standing problem and essential for further development of the much more effective catalytic asymmetric reactions of the ene-imines. we carried out molecular orbital calculations and revealed that the experimentally observed regioselectivity is rationalized by the relative magnitude of the LUMO coefficients.
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