Synthesis of Functionalized Epoxides by Copper-Catalyzed Alkylative Epoxidation of Allylic Alcohols with Alkyl Nitriles

A copper-catalyzed oxyalkylation of allylic alcohols using nonactivated alkyl nitriles as reaction partners was developed. A sequence involving generation of an alkyl nitrile radical followed by its addition to a double bond and a copper-mediated formation of C(sp(3))-O bond was proposed to account for the reaction outcome. The protocol provided an efficient route to functionalized tri- and tetrasubstituted epoxides via formation of a C(sp(3))C(sp(3)) and a C(sp(3))-O bond with moderate to excellent diastereoselectivity.