Regio- and Stereoselective Dehydrogenative Silylation and Hydrosilylation of Vinylarenes Catalyzed by Ruthenium Alkylidenes.

Development of regio- and stereoselective dehydrogenative silylation and hydrosilylation of vinylarenes with alkoxysilanes, catalyzed by ruthenium alkylidenes, is described. Varying L- and X-type ligands on ruthenium alkylidenes permits selective access to either (E)-vinylsilanes or β-alkylsilanes with high regio- and stereocontrol. cis,cis-1,5-Cyclooctadiene was identified as the most effective sacrificial hydrogen acceptor for the dehydrogenative silylation of vinylarenes, which allows use of a nearly equimolar ratio of alkenes and silanes.