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

Eşsiz S., BOZKAYA U.

Journal of Organic Chemistry, vol.85, no.15, pp.10136-10142, 2020 (SCI-Expanded) identifier identifier

  • Publication Type: Article / Article
  • Volume: 85 Issue: 15
  • Publication Date: 2020
  • Doi Number: 10.1021/acs.joc.0c01472
  • Journal Name: Journal of Organic Chemistry
  • Journal Indexes: Science Citation Index Expanded (SCI-EXPANDED), Scopus, Academic Search Premier, BIOSIS, Chemical Abstracts Core, Chimica, Compendex, EMBASE, MEDLINE
  • Page Numbers: pp.10136-10142
  • Hakkari University Affiliated: No


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.