Silver-catalyzed anionic [3 + 2] cycloaddition of benzyl isocyanides with polyfluoroalkylchromones and pyrones:...

A silver-catalyzed anionic [3 + 2] cycloaddition of benzyl isocyanides has been developed, providing direct one-pot access to 2-arylpyrroles - a privileged scaffold pervasive in medicinal chemistry and functional materials. Despite high demand, general one-step routes to this motif remain rare, and the synthetic potential of benzyl isocyanides in cycloaddition chemistry has been severely limited by their low reactivity. We herein show that the combination of AgOAc (10 mol %) and KOt-Bu efficiently promote the reaction of benzyl isocyanides with 2-polyfluoroalkylchromones and 6-(trifluoromethyl)-4H-pyrones, delivering 2-arylpyrroles in yields of up to 83% with complete chemo- and regioselectivity. The protocol is operationally simple and extends readily to chromones and pyrones lacking a trifluoromethyl group, demonstrating a broad substrate scope. This work establishes a practical catalytic entry to an important heterocyclic class and unlocks the underexplored utility of benzyl isocyanides in cycloaddition reactions.