N‑Heterocyclic Carbene-Catalyzed Truce–Smiles Rearrangement of N‑Arylacrylamides via the Cleavage of Unactivated C(aryl)–N Bonds

We report on the N-heterocyclic carbene (NHC)-catalyzed Truce–Smiles rearrangement of aniline derivatives, in which an unactivated C­(aryl)–N bond is cleaved, leading to the formation of a new C­(aryl)–C bond. The key to the success of this reaction is the utilization of a highly nucleophilic NHC, which enables the formation of a highly nucleophilic ylide intermediate that is generated from an α,β-unsaturated amide.