| Project/Area Number |
15K14929
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| Research Category |
Grant-in-Aid for Challenging Exploratory Research
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| Allocation Type | Multi-year Fund |
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| Research Field |
Chemical pharmacy
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| Research Institution | Hiroshima University |
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Principal Investigator |
Takeda Kei 広島大学, 医歯薬保健学研究院(薬), 教授 (30135032)
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| Co-Investigator(Kenkyū-buntansha) |
佐々木 道子 広島大学, 医歯薬保健学研究院(薬), 准教授 (30379888)
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| Project Period (FY) |
2015-04-01 – 2017-03-31
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| Project Status |
Completed (Fiscal Year 2016)
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| Budget Amount *help |
¥3,640,000 (Direct Cost: ¥2,800,000、Indirect Cost: ¥840,000)
Fiscal Year 2016: ¥1,820,000 (Direct Cost: ¥1,400,000、Indirect Cost: ¥420,000)
Fiscal Year 2015: ¥1,820,000 (Direct Cost: ¥1,400,000、Indirect Cost: ¥420,000)
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| Keywords | 不斉反応 / アレン / シアニドイオン / キラルカルバニオン / 相間移動触媒 / 有機合成 |
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| Outline of Final Research Achievements |
Reactions of γ-bromo-α,β,γ,δ-unsaturated acylsilanes with KCN and quaternary ammonium bromide derived from cinchona alkaloids afforded nonracemic 2-cyano-2-siloxyvinylallenes via a tandem process that involves a nucleophilic attack of a cyanide ion and a Brook rearrangement-induced conjugate vinylic 1,4-elimination. Based on this result and on the stereochemical outcome of the reaction using hydride ion as a chiral source, we propose a reaction pathway in which a Brook rearrangement-mediated vinylic conjugate 1,4-elimination occurs in a syn alignment between the C-Br bond and C-Si bond in the silicate intermediate. The finding that reactions using a chiral cyanide ion source provided nonracemic allene derivatives opens a new perspective in the enantioselective synthesis of highly functionalized allene derivatives.
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