A laterally-fused N-heterocyclic carbene framework from polysubstituted aminoimidazo[5,1-]oxazol-6-ium salts.

A polysubstituted 3-aminoimidazo[5,1-]oxazol-6-ium framework has been accessed from a new nitrenoid reagent by a two-step ynamide annulation and imidazolium ring-formation sequence. Metalation with Au(I), Cu(I) and Ir(I) at the C2 position provides an L-shaped NHC ligand scaffold that has been validated in gold-catalysed alkyne hydration and arylative cyclisation reactions.