Stereoselective Preparation of 1-Siloxy-1-alkenylcopper Species by 1,2-C^sp2-to-O Silyl Migration of Acylsilanes

Akira Tsubouchi, Kotaro Onishi and Takeshi Takeda*

*Department of Applied Chemistry, Graduate School of Engineering, Tokyo University of Agriculture and Technology, Koganei, Tokyo 184-8588, Japan, Email: takeda-tcc.tuat.ac.jp

A. Tsubouchi, K. Onishi, T. Takeda, J. Am. Chem. Soc., 2006, 128, 14268-14269.

DOI: 10.1021/ja0658822

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Abstract

1-Siloxy-1-alkenylcopper species were generated by 1,2-C^sp2-to-O silyl migration of the copper enolates of acyltriphenylsilanes. The alkenylcopper species reacted with methyl, benzyl, allylic, tributylstannyl halides and in the presence of Pd(0) catalyst with aryl and alkenyl iodides to give geometrically pure (Z)-enol silyl ethers.

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proposed mechanism

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Key Words

Silyl enol ethers, Ketones, Arylketones, Enones, Brook Rearrangement

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ID: J48-Y2006-3590