Cycloaddition of sulfonyl azides and cyanogen azide to enamines. Quantum-chemical calculations concerning the spontaneous rearrangement of the adduct into ring-contracted amidines

Enamines derived from cyclic ketones react with arenesulfonyl azides and cyanogen azide, mainly via ring contraction, with formation of the corresponding amidines. The mechanism of this efficient rearrangement, which has not been investigated experimentally, was determined with the aid of quantum-chemical calculations. In the transition state, from the intermediate 5-amino-v-triazolines, the loss of dinitrogen and a cyclic rearrangement occurred in one-step in a quite synchronous manner with a very low transition state energy.