1,4‐Aminoarylation of Butadienes via Photoinduced Palladium Catalysis

Abstract A visible‐light‐induced, three‐component palladium‐catalyzed 1,4‐aminoarylation of butadienes with readily available aryl halides and aliphatic amines has been developed, affording allylamines with excellent E ‐selectivity. The reaction exhibits exceptional control over chemo‐, regio‐, and stereoselectivity, a broad substrate scope, and high functional group compatibility, as demonstrated by the late‐stage functionalization of bioactive molecules. Mechanistic investigations are consistent with a photoinduced radical Pd(0)‐Pd(I)‐Pd(II)‐Pd(0) Heck‐Tsuji–Trost allylation cascade.