Mechanistic Studies of the CuH-Catalyzed Synthesis of α-Hydroxyallenes

Abstract

The copper hydride catalyzed SN2′ reduction of propargyl oxiranes is an efficient method for the diastereoselective synthesis of α-hydroxyallenes. Herein, we represent a detailed computational study of this reaction using density functional theory (DFT), supported by kinetic investigations. The calculations partially validate the previously proposed reaction mechanism and explain the high anti stereoselectivity of the reaction arising from a diffusion-controlled Lewis acid activation of the epoxide–Cu–hydride complex.