Stereoselective synthesis of vinylsilanes by a gold(I)-catalyzed acetylenic sila-cope rearrangement.

Cationic tri-tert-butylphosphinegold(I) serves as a catalyst in the sila-Cope rearrangement of acetylenic allylsilanes. When phenol is employed as a nucleophile, the reaction allows for the stereoselective synthesis of vinylsilanes. Alternatively, use of methanol as a nucleophile leads to cyclic vinylsilanes, which can be viewed as latent vinylsilanes that are revealed on treatment with a mild Lewis acid. Thus, both of these reagents serve as useful reagents for stereoselective synthesis of trisubstituted olefins through transition-metal-catalyzed cross-coupling reactions.