Acid/Base‐Co‐catalyzed Direct Oxidative α‐Amination of Cyclic Ketones: Using Molecular Oxygen as the Oxidant

A novel acid/base‐co‐catalyzed direct intermolecular α‐amination of various cyclic ketones has been developed for the first time. The reaction employs molecular oxygen as the sole oxidant under metal‐free conditions. The reaction tolerates a wide range of various anilines, especially primary diamine derivatives, and provides a simple and efficient method for the constructions of α‐amino enones and benzodiazepine derivatives in a single step.