Photoredox andCobalt-Catalyzed Markovnikov-SelectiveRadical 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.