Ligand-Controlled Regiodivergent Silylation of Allylic Alcohols by Ni/Cu Catalysis for the Synthesis of Functionalized Allylsilanes

The first Ni/Cu-catalyzed regiodivergent synthesis of allylsilanes directly from allylic alcohols through modulating the steric and electronic properties of the ligands on the nickel catalyst has been developed. Good yields and excellent selectivity were obtained regardless of whether linear or α-branched allylic alcohols were utilized. Mechanistic studies indicate that an allyloxyboronate species is formed during the reaction, which likely serves as an activated intermediate toward the oxidative addition of the C­(allyl)–O bond.