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(sp3)–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(sp3)–C­(sp3) and a C­(sp3)–O bond with moderate to excellent
diastereoselectivity.