Rhodium-Catalyzed O-Silylation of Alcohols with Vinyl Silanes

Significance The O-silylation of alcohols is one of the most widely used protection methods in organic synthesis. Herein, a new interesting modification of this method, using vinyl silanes as silicium source, is described. The reaction can be performed with only 0.01 mol% of the commercial rhodium catalyst. Benzylic, primary, secondary, and tertiary alcohols can be successfully silylated. This reaction represents also a useful method for the preparation of polyalkoxysilanes from polyvinylsilanes, suitable for chromatographical purification.