Frustrated Lewis Pairs Catalyse the Solvent‐assisted Synthesis of Azoles from ortho‐Substituted Anilines, CO2 and H2

Synthesizing azoles from ortho-substituted anilines, CO2 and H2 has proved difficult due to the low nucleophilicity of which hinders their N-formylation, i.e., first step reaction. Herein, we demonstrate that R3SnX Lewis acids (LA), N-methylmorpholine (NMM) or DBU polyethyleneimine (PEI) N-formylmorpholine efficiently catalyse synthesis benzimidazole other by reductive coupling nucleophilic amine-based solvents, PEI morpholine, followed in-situ transfer formyl group appropriate aniline. Under these reaction conditions, spontaneous cyclization N-formylated intermediate yields corresponding azole in up 98% yield.