Development of Enantioselective Synthesis of Allenes Using Chirality Transfer from a Chiral Carbanion
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 |
Research Field |
Chemical pharmacy
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Research Institution | Hiroshima University |
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 |
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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Report
(3 results)
Research Products
(26 results)
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[Presentation] Fitst Total Synthesis of Prunustatin A2015
Author(s)
Shuhei Yamkoshi, Masako Okamoto, Eiji Kawanishi, Michiko Sasaki, Kei Takeda
Organizer
The 13th International Kyoto Conference on New Aspects of Organic Chemistry
Place of Presentation
Kyoto
Year and Date
2015-11-09
Related Report
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