Gold-Catalyzed Intramolecular Allylation of Silyl Alkynes Induced by Silane Alcoholysis

Abstract

The activation of alkynyl allyl silanes with a cationic gold catalyst in the presence of alcohols provides vinyl silanes that contain the allyl group at the β-position and the alkoxysilyl group in cis-orientation. The bond reorganization process is most consistent with the involvement of a carbocationic intermediate, which undergoes a nucleophilic attack by an alcohol selectively at the silicon center. The cis-vinyl silyl ether products can be further elaborated by ring-closing and cross metathesis to form more substituted 1,4-dienyl silanes.