A novel and efficient method for the synthesis of structurally diverse imidazoles through a multicomponent reaction involving an azirine, an amine, and an aldehyde is described. The method is simple and environmentally benign, producing multifunctionalized imidazoles in moderate‐to‐good yields and in a regioselective manner, which was demonstrated by NMR experiments and X‐ray analysis. A mechanism is proposed in which the amine participates not only as a reactant, but also as a nucleophilic reaction promoter.
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