J. Am. Chem. Soc., 127 (28), 10028 -10038, 2005. 10.1021/ja051578h S0002-7863(05)01578-7
Web Release Date: June 18, 2005

Copyright © 2005 American Chemical Society

An Alkyne Hydrosilylation-Oxidation Strategy for the Selective Installation of Oxygen Functionality

Barry M. Trost,* Zachary T. Ball, and Kai M. Laemmerhold

Contribution from the Department of Chemistry, Stanford University, Stanford, California 94305-5080

bmtrost@stanford.edu

Received March 11, 2005

Abstract:

Alkynes bearing propargylic, homopropargylic, and bishomopropargylic hydroxyl groups are shown to serve as precursors for ketone or -hydroxy ketone functionality. The approach hinges on the intermediacy of vinylsilanes created through regioselective hydrosilylation catalyzed by the complex [Cp*Ru(MeCN)3]PF6. Several oxidative pathways of linear and cyclic vinylsilanes are studied, and the possibility of diastereoselective epoxidation of cyclic vinylsilanes is demonstrated. The sequences constitute the equivalent of stereoselective aldol, homo-aldol, and bishomo-aldol type processes. The method is applied to a short synthesis of the piperidine alkaloid, spectaline.

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