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Disclosed herein is the unique conjugative role of N-heterocyclic carbene (NHC) ligands as a directing group in aromatic C–H activation, coupled with a facile NHC–alkenyl annulative reductive elimination which guided the RhIII-catalyzed intermolecular annulations of imidazolium salts and alkynes under ambient conditions leading to structurally important imidazo[1,2-a]quinolinium motifs.

Graphical abstract: Exploring a unique reactivity of N-heterocyclic carbenes (NHC) in rhodium(iii)-catalyzed intermolecular C–H activation/annulation

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