Synergistic Ni/Cu catalyzed migratory arylsilylation of terminal olefins

Abstract

Synthesis of organosilanes from alkenes is a very important topic owing to their wide applications. A Ni/Cu dual metal-catalyzed arylsilylation of terminal alkenes, featuring migratory selectivity, has been developed. A wide diversity of aliphatic silanes have been prepared from terminal alkenes, aryl halides and Suginome's reagent. This protocol is highlighted by excellent regioselectivity, mild reaction conditions and good functional group tolerance. In addition to benzylic positions, carbon-carbon bonds can also be constructed at allylic positions. Preliminary mechanistic studies suggest that the copper cocatalyst promotes the transmetalation of Suginome's reagent, and the addition of a PyrOx ligand inhibits the formation of side-products from the carbon-Heck pathway. Moreover, studies toward the nature of the PyrOx ligand revealed that the steric hindrance of the oxazoline moiety greatly affects the chain-walking process, but not the arylation step.

Keywords: Alkene difunctionalization; Arylsilylation; Metal migration; Regioselectivity; Synergistic catalysis.