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

EŞSİZ S., BOZKAYA U.

JOURNAL OF ORGANIC CHEMISTRY, vol.85, no.15, pp.10136-10142, 2020 (SCI-Expanded) identifier 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
  • Hacettepe University Affiliated: Yes

Abstract

A computational study of N-hydroxyphthalimidecatalyzed 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 SO 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.