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. 2005 Dec 21;127(50):17644-55.
doi: 10.1021/ja0528580.

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

Barry M Trost  1 , Zachary T Ball
Affiliations

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

Barry M Trost et al. J Am Chem Soc. .

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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Figures

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Figure 1
Figure 1
Calculated transition state structures.
Figure 2
Figure 2
A proposed mechanism for transition addition without cis-trans isomerization.
Scheme 1
Scheme 1
Synthetic utility of benzyldimethylsilanes.
Scheme 2
Scheme 2
Solvent optimization.
Scheme 3
Scheme 3
Deuterium labeling of terminal alkynes.
Scheme 4
Scheme 4
Failed attempts at propargylic alcohol hydrosilylation.
Scheme 5
Scheme 5
Chemoselectivity among alkynes.
Scheme 6
Scheme 6
Synthesis of tethered Diels-Alder substrates with hydrosilylation.
Scheme 7
Scheme 7
Alkyne hydrosilylation to build more complex substrates for silicon-tethered Diels-Alder reactions.
Scheme 8
Scheme 8
Hydrosilylation-metathesis for cyclic vinylsilane formation.
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