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

The complex [Cp*Ru(MeCN)3]PF6 is shown to catalyze the hydrosilylation of a wide range of alkynes. Terminal alkynes afford access to α-vinylsilane products with good regioselectivity. Deuterium labeling studies indicate a clean trans addition process is at work. The same complex is active in interna...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2005-12, Vol.127 (50), p.17644-17655
Main Authors: Trost, Barry M, Ball, Zachary T
Format: Article
Language:English
Subjects:
Alkynes - chemistry
Catalysis
Chemistry
Exact sciences and technology
Kinetics and mechanisms
Models, Molecular
Organic chemistry
Propanols - chemistry
Reactivity and mechanisms
Ruthenium - chemistry
Silanes - chemical synthesis
Thermodynamics
Vinyl Compounds - chemical synthesis
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Summary:The complex [Cp*Ru(MeCN)3]PF6 is shown to catalyze the hydrosilylation of a wide range of alkynes. Terminal alkynes afford access to α-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 α,β-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.
ISSN:0002-7863
1520-5126
DOI:10.1021/ja0528580