Cobalt/Photoredox‐Catalyzed Regioselective Hydroamination of 1,3‐Dienes With Free Amines

ABSTRACT Allylic amines are ubiquitous motifs in pharmaceuticals, agrochemicals, and materials, yet direct access to regioisomeric variants remains limited. Here, we report a dual cobalt/photoredox catalytic platform that enables regioselective 1,4‐hydroamination of acyclic 1,3‐dienes. The transformation proceeds via a metal−hydride hydrogen atom transfer (MHAT) from a Co─H species, followed by a radical‐polar crossover nucleophilic amination process, which delivers ( E )‐allylamines under mild conditions, with broad functional group tolerance, compatibility with complex molecules, and scalability that enables the incorporation of anilines and even more nucleophilic and basic dialkyl amines as feedstocks and expands the synthetic toolbox for alkene hydrofunctionalization.