Regio- and stereoselective trans-silylvinylation of internal alkynes catalyzed by RuHCl(CO)(PCy3)2

We report a novel trans-silylvinylation of internal alkynes catalyzed by RuHCl(CO)(PCy3)2. This method represents a highly regio- and stereoselective synthesis of functionalized dienes by means of an efficient tandem alkyne trans-silylruthenation, followed by an addition to acrylates. The products are further transformed by Pd-catalyzed cross couplings and carbonylations to afford dienes with significantly increased molecular complexity.