Iron‐Catalyzed Haloaminative Cyclization of Aminoallenes via CN Bond Activation

The selective cleavage and efficient transformation of CN bonds in tertiary amines remain a significant challenge due to their high bond dissociation energy and inherent stability. Herein, an iron‐catalyzed haloaminative cyclization of tertiary amine‐tethered allenes with electrophilic halogen sources is reported, in which the benzylic CN bond is selectively broken by the in situ formation of quaternary ammonium salts. This method features concise reaction protocols, broad substrate scopes, enabling the rapid acquisition of diverse N ‐heterocyclic derivatives containing the vinyl halide moieties. What's more, the presence of vinyl halide groups facilitates late‐stage diversification through a series of downstream cross‐coupling reactions.