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

Abstract Synthesizing azoles from ortho ‐substituted anilines, CO 2 and H 2 has proved difficult due to the low nucleophilicity of anilines, which hinders their N‐formylation, i. e., the first step of the reaction. This study demonstrates that R 3 SnX Lewis acids (LA), N‐methylmorpholine (NMM) or DBU and polyethyleneimine (PEI) or N‐formylmorpholine efficiently catalyse the synthesis of benzimidazole and other azoles from ortho ‐substituted anilines, CO 2 and H 2 by reductive coupling of CO 2 to nucleophilic amine‐based solvents, PEI or morpholine, followed by in‐situ transfer of the formyl group to the appropriate ortho ‐substituted aniline. Under these reaction conditions, spontaneous cyclization of the N‐formylated intermediate yields the corresponding azole in up to 98 % yield.