N-Heterocyclic Carbene-Catalyzed Truce–Smiles Rearrangement of <i>N</i>-Arylacrylamides via the Cleavage of Unactivated C(aryl)–N Bonds
Kosuke Yasui, Miharu Kamitani, Hayato Fujimoto, Mamoru Tobisu
Abstract
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.
Topics & Concepts
CarbeneChemistryArylYlideNucleophileSmiles rearrangementCleavage (geology)Bond cleavageCatalysisAnilineAmideMedicinal chemistryStereochemistryOrganic chemistryAlkylFracture (geology)Geotechnical engineeringEngineeringCatalytic Cross-Coupling ReactionsN-Heterocyclic Carbenes in Organic and Inorganic ChemistryCatalytic C–H Functionalization Methods