ComputationalStudy for the ReactionMechanism of N ‑Hydroxyphthalimide-Catalyzed Oxidative Cleavage of Alkenes

A computational study of N-hydroxyphthalimide-catalyzed aerobic oxidative cleavage of alkenes is carried out employing density functional theory and high-level coupled-cluster methods, such as coupled-cluster singles and doubles with perturbative triples [CCSD­(T)]. Our results demonstrate that the reaction proceeds through the alkoxyl radicals, as opposed to the mechanism suggested by Jiao and co-workers (Org. Lett. 2012, 14, 4158–4161), in which the reaction proceeds via formation of the dioxetane ring. The barriers for the formation of dioxetane derivatives are computed to be higher than 50 kcal mol–1, while the barriers for the formation of alkoxyl radicals are as low as 13 kcal mol–1. Our results also demonstrate that epoxide derivatives can be formed as intermediates or byproducts under the reaction conditions.