Abstract A new method for the preparation of 1, 4, 5-trisubstituted (imidazol-2-yl) acetates, based on the reaction of the corresponding imidazole 3-oxides with dimethyl acetylenedicarboxylate (DMAD) is described. Formation of the products is rationalized by a formal 1, 3-dipolar cycloaddition and subsequent oxaloyl cleavage.