Ni/Cu-catalyzed silylation of allylic alcohol: Theoretical studies on the mechanisms, regioselectivity, and role of ligand

Abstract

Abstract The mechanisms of the Ni/Cu-catalyzed silicification of allyl alcohols were investigated by employing the density functional theory (DFT) calculations. Five main steps are included in the reaction: initialization of reactants, oxidative addition, transmetalation, reductive elimination and regeneration of Cu catalyst. Among them, oxidative addition involving the initialized allyl alcohol, Ni catalyst and Cu catalyst is calculated to be the rate- and regioselectivity-determining step. The Cu catalyst employed in the experiment can improve both the stability and activity of the catalyst. In this reaction, different ligand would lead to different product. The origins of the ligand-controlled regioselectivity were clarified through our calculations. By using PEt3 ligand, the formed branched allylsilanes product was caused by the steric effects. While the 8-(diphenylphosphanyl)quinoline ligand would lead to the linear product due to the existed steric repulsion and coordination interaction.