Computational Study for the Reaction Mechanism of N -Hydroxyphthalimide-Catalyzed Oxidative Cleavage of Alkenes

The Journal of Organic Chemistry
Selçuk Eşsiz, Uğur Bozkaya

Abstract

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.

References

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