Catalyst-Controlled, Regiodivergent Aminooxygenation Reactions of Dienes

We report a method for an aerobic, regiodivergent aminooxygenation of dienes via catalyst control. A simple switch in the copper catalyst source allows for selective access to either the 1,2- or 1,4-aminooxygenated product from a single starting material. Mechanistic studies indicate that the coordinating ligand on the copper salt is responsible for the divergent regiochemical outcomes and that the origin of regiodivergence lies in competing mechanisms for oxygen delivery to the carbon-centered radical intermediate.