Alkyne Hydrosilylation Catalyzed by a Cationic Ruthenium Complex: Efficient and General Trans Addition

Overview

Journal J Am Chem Soc

Publisher American Chemical Society

Specialty Chemistry

Date 2005 Dec 15

PMID 16351094

Citations 52

Authors

Barry M Trost

Zachary T Ball

Affiliations

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Abstract

The complex [Cp*Ru(MeCN)3]PF6 is shown to catalyze the hydrosilylation of a wide range of alkynes. Terminal alkynes afford access to alpha-vinylsilane products with good regioselectivity. Deuterium labeling studies indicate a clean trans addition process is at work. The same complex is active in internal alkyne hydrosilylation, where absolute selectivity for the trans addition process is maintained. Several internal alkyne substrate classes, including propargylic alcohols and alpha,beta-alkynyl carbonyl compounds, allow regioselective vinylsilane formation. The tolerance of a wide range of silanes is noteworthy, including alkyl-, aryl-, alkoxy-, and halosilanes. This advantage is demonstrated in the direct synthesis of triene substrates for silicon-tethered intramolecular Diels-Alder cycloadditions.

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