Insights into the Mechanism of O(³P)-Mediated Oxidation of Alkenes through Kinetic Isotope Effects and Computational Modeling.

ABSTRACT: Photodeoxygenation of aryl sulfoxides, such as dibenzothiophene S-oxide (DBTO), produces atomic oxygen [O(³P)] in solution. The mechanism of alkene oxidation with O(³P) remains uncertain. To address this, the current study utilized kinetic isotope effects (KIEs) and computational approaches to study the reaction of O(³P) with styrene and its isotopologues. Notably, the 2° CH/D KIE at the internal and terminal carbons of the reactive π-bond was ∼1.00 and ∼0.87, respectively. These findings indicate a terminal addition of O(³P) to the π-bond, supporting a stepwise oxidation pathway. Both epoxide and aldehyde products go through the same rate-determining transition state and then diverge based on the intermediate conformation. The O-C-C-C dih

SUBMITTER: Maness PF 

PROVIDER: S-EPMC10846523 | biostudies-literature | 2024 Feb

REPOSITORIES: biostudies-literature