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.
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