| Project/Area Number |
04640520
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| Research Category |
Grant-in-Aid for General Scientific Research (C)
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| Allocation Type | Single-year Grants |
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| Research Field |
有機化学一般
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| Research Institution | Tokushima Bunri University |
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Principal Investigator |
TSUNODA Tetsuo Tokushima Bunri University, Faculty of Pharmaceutical Sciences, Associate Professor, 薬学部, 助教授 (00172049)
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| Project Period (FY) |
1992 – 1993
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| Project Status |
Completed (Fiscal Year 1993)
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| Budget Amount *help |
¥1,900,000 (Direct Cost: ¥1,900,000)
Fiscal Year 1993: ¥300,000 (Direct Cost: ¥300,000)
Fiscal Year 1992: ¥1,600,000 (Direct Cost: ¥1,600,000)
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| Keywords | Asymmetric Aza-Claisen Rearrangement / Amide enolates / Stereoselective synthesis / (-)-Verrucarinolactone / D-allo-Isoleucine / (-)-Isoiridomyrmecin |
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| Research Abstract |
The Ireland-Claisen rearrangement of the enolates of allylesters, frequently used for the stereocontrolled C-C bond formation, is not suited for the substrate-controlled asymmetric induction. In order to cover the shortcoming, we investigated the thermal rearrangement of amide enolates and found that 1) the enolate derived from N-(2E)-buteny1-N-buty1propanamide rearranged with excellent intermal asymmetric induction (syn : anti = 199 : 1), that 2) the reaction of those containing chiral alkyl groups on the nitrogen proceeded with high selectivity (up to 19 : 1) in relative asymmetric induction, and that 3) the rearrangement can satisfactorily be extended to the acetamides with a heteroatom at the alpha-position. 4) Utilyzing the reaction, (-)-verrucarinolactone, D-allo-isoleucine, and (-)-isoiridomyrmecin were synthesized with excellent stereoselectivity in short steps.
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