Synthesis of Homoallylic Amines by Radical Allylation of Imines with Butadiene under Photoredox Catalysis

Abstract Ionic (2 e − ) nucleophilic addition of allylmetal regents to imines dominates the synthesis of homo‐allyl amine; however, single electron (1 e − ) mediated imine allylation with feedstocks butadiene as an alternative allyl source remains unexplored. In this work, we report a conceptually different radical–radical cross‐coupling strategy for the synthesis of a homoallyl amine between an α‐amino alkyl radical and a transient allylic radical. This metal‐free method provided a novel approach for the synthesis of homoallylic amines (>80 examples) from readily available materials with excellent regioselectivity and exceptional broad functional group compatibility.