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Alkyne hydrosilylation catalyzed by a cationic ruthenium complex: efficient and general trans addition.

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.

SUBMITTER: Trost BM

PROVIDER: S-EPMC2532823 | biostudies-literature | 2005 Dec

REPOSITORIES: biostudies-literature

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Alkyne hydrosilylation catalyzed by a cationic ruthenium complex: efficient and general trans addition.

Trost Barry M BM Ball Zachary T ZT

Journal of the American Chemical Society 20051201 50

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 ...[more]

PMID: 16351094

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