A computational study on the competing intramolecular amidation and aziridination reactions catalyzed by dirhodium tetracarboxylate

The yields of amides and aziridines for two cases of dirhodium tetracarboxylate-catalyzed competing amidation and aziridination reactions were successfully interpreted by density functional calculations. For each reaction, four reaction pathways were examined structurally and energetically. The relative reaction rates of different reaction pathways were calculated from the relative free energy of activations for all of the four pathways. Our results may help synthetic chemists better design the substrates and scaffolds of catalyst ligands, for transition metal catalyzed amidation and aziridination reactions.