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 copper catalyst source allows for selective access to either 1,2- or 1,4-aminooxygenated product from a single starting material. Mechanistic studies indicate that the coordinating ligand on the starting copper salt is responsible for the divergent regiochemical outcomes, and that the origin of regiodivergence lies in competing mechanisms for oxygen delivery to the cyclized, carbon-centered radical intermediate.