Two Unusual, Competitive Mechanisms for (2-Ethynylphenyl)triazene Cyclization:  Pseudocoarctate versus Pericyclic Reactivity

The cyclization of (2-ethynylphenyl)triazenes in ODCB at 200 °C gives exclusively cinnolines, whereas addition of CuCl to 1,2-dichloroethane solutions of the triazenes at 50 °C results in the sole formation of isoindazoles. DFT calculations and deuterium labeling studies suggest the intermediacy of a 3-dehydrocinnolinium ion, produced through a pericyclic transition state. Calculations and trapping studies strongly implicate a carbene intermediate in isoindazole formation, which proceeds through a pseudocoarctate transition state.