Construction of N‑Polyheterocycles by N‑Heterocyclic Carbene Catalysis via a Regioselective Intramolecular Radical Addition/Cyclization Cascade

N-Polyheterocycles are rapidly accessed by N-heterocyclic carbene (NHC) catalysis through regioselective sequential radical addition/cyclization in the absence of any metals or oxidants. The transformation occurs under mild conditions and enjoys a wide substrate scope with excellent functional group compatibility. Furthermore, a gram-scale synthesis is also conducted. Preliminary mechanistic studies reveal the potential involvement of an NHC radical cation intermediate.