Highly Chemoselective and Stereoselective Synthesis of <i>Z</i>-Enol Silanes

Abstract

Three-component nickel-catalyzed couplings of enals, alkynes, and silanes have been developed as a new entry to enol silanes. The enol silane and a trisubstituted alkene are both formed with >98:2 stereoselectivity, and the reaction tolerates a broad range of functionality including aldehydes, ketones, esters, free hydroxyls, and basic secondary amines. A mechanistic pathway involving the formation of a metallacycle that possesses an eta1 nickel O-enolate motif explains the high level of stereoselection.