ABSTRACT Multi‐component reactions (MCRs) are effective for rapidly assembling complex structures in a single synthetic step. We present a visible‐light‐driven, metal‐ and photosensitizer‐free four‐component reaction that synthesizes multifunctionalized homoallylic amines through synergistic radical coupling. This approach utilizes in situ generated α‐amino alkyl radicals, formed via photoreduction of imine umpolung, and persistent allylic radicals from NHP‐esters and 1,3‐dienes, facilitating efficient C─C bond formation under mild conditions. Its applicability in natural product derivatizations underscores its value in complex molecular synthesis. Mechanistic studies confirm a radical–radical cross‐coupling pathway.
Zhang et al. (Fri,) studied this question.