Synthesis of α-Vinyltrialkoxysilanes via Nickel-Mediated Cross-Electrophile Coupling Reactions.

Abstract

Vinyltrialkoxysilanes are indispensable for organic synthesis, particularly cross-coupling reactions. Hydrosilylation of alkynes inevitably yields α- and β-isomers of vinyltrialkoxysilanes even with complex ligands and catalysts, limiting its usage in organic synthesis. We report the synthesis of α-vinyltrialkoxysilanes via cross-electrophile C(sp2)-C(sp2) coupling of bromoalkenes. The method is quite compatible with functional groups under milder reaction conditions. The gram-scale synthesis of most substrates is impressive. The intermediacy of vinyl iodide and radical escape rebound path are supported by mechanistic studies.