Photoredox and Cobalt-Catalyzed Markovnikov-Selective Radical Hydroamination of Unactivated Alkenes with Anilines

The intermolecular hydroamination of unactivated alkenes with simple amines continues to be an attractive and challenging undertaking in organic synthesis. The current state-of-the-art strategies for photocatalyzed hydroamination of unactivated alkenes with amines usually commence with the formation of a C-N bond, thereby delivering exclusively the anti-Markovnikov products. We herein reported a facile and mild intermolecular Markovnikov hydroamination of unactivated alkenes with anilines through photoredox and cobalt-catalyzed hydrogen atom transfer followed by a radical-polar crossover nucleophilic amination process. The reaction features a wide substrate scope, good functional group tolerance, and good to excellent yields. Application of this reaction to late-stage functionalization of relatively complex natural products and bioactive molecules further increases the utility of the developed methodology.