Quantum chemical studies of carbocations from oxidized metabolites of aza-polycyclic aromatic hydrocarbons.

BOROSKY, GABRIELA L.; LAALI, KENNETH K.

Recent Developments in Carbocation and Onium Ion Chemistry

American Chemical Society

Año: 2007; p. 329 - 363

Model computational studies aimed at understanding structure-reactivity relationships and substituent effects on carbocation stability for aza-PAHs derivatives were performed by density functional theory (DFT). Comparisons were made with the biological activity data when available. Protonation of the epoxides and diol epoxides, and subsequent epoxide ring opening reactions were analyzed for several families of compounds. Bay-region carbocations were formed via the O-protonated epoxides in barrierless processes. Relative carbocation stabilities were determined in the gas phase and in water as solvent (by the PCM method).