Highly Selective Preparation of (E)- and (Z)- Silyl Enol Ethers from Wittig Reaction of Salt-Free Phosphonium Ylide Generated by 1,2-Brook Rearrangement

Research Project

Project/Area Number	26860011
Research Category	Grant-in-Aid for Young Scientists (B)
Allocation Type	Multi-year Fund
Research Field	Chemical pharmacy
Research Institution	University of Toyama
Principal Investigator	Minato Daishiro 富山大学, 大学院医学薬学研究部(薬学), 助教 (80610914)
Project Period (FY)	2014-04-01 – 2016-03-31
Project Status	Completed (Fiscal Year 2015)
Budget Amount *help	¥3,900,000 (Direct Cost: ¥3,000,000、Indirect Cost: ¥900,000) Fiscal Year 2015: ¥1,950,000 (Direct Cost: ¥1,500,000、Indirect Cost: ¥450,000) Fiscal Year 2014: ¥1,950,000 (Direct Cost: ¥1,500,000、Indirect Cost: ¥450,000)
Keywords	Brook転位 / Wittig反応 / ホスフィン / イリド / 炭素間結合反応 / シリルエノールエーテル / 炭素間結合形成反応
Outline of Final Research Achievements	The target of this study is to develop new methodologies for the molecular transformation based on the intramolecular silyl group rearrangement reaction, so-called Brook rearrangement. In searching for various conditions, the reaction of acylsilanes with phosphine nucleophiles which afforded phosphonium ylides through 1,2-Brook rearrangement was found. A Wittig reaction of the resulting phosphonium ylides and aldehydes or imines proceeded successively and afforded silyl enol ethers with high stereoselectivity.