In the present work we describe the synthetic routes for preparing unprecedented 2,5-diamido 5-membered heterocycles based on the thiophene, pyrrole and furan rings exploiting Curtius-like rearrangement reactions. Conformational analysis performed for the 2,5-diamidothiophene derivatives displayed a “closed” conformation, in which the two carbonyl O atoms are in close contact with the thiophen S atom.