Copper-Catalyzed 1,2-Aminocyanation of Unactivated Alkenes via Cyano Migration.

A copper-catalyzed aminocyanation of alkenes has been achieved through distal cyano migration using O-benzoylhydroxylamines and N-fluorobenzenesulfonimides. This method offers a rapid approach to generate diverse β-amino and β-sulfonimido nitriles. These reactions feature mild conditions, tolerance of sensitive functional groups, and excellent regioselectivity. Mechanistic studies suggest that these transformations are initiated by a copper-catalyzed amination step followed by a cyano migration step.