Dimethyldioxirane: Mechanism of benzaldehyde oxidation

✍ Scribed by A.L. Baumstark; M. Beeson; P.C. Vasquez

• Publisher: Elsevier Science
• Year: 1989
• Tongue: French
• Weight: 317 KB
• Volume: 30
• Category: Article
• ISSN: 0040-4039
• DOI: 10.1016/s0040-4039(01)93801-8

✦ Synopsis

Under inert atmosphere, dimethyldioxirane 1 converts benzaldehydes solely to the corresponding acids; the reaction is insensitive to electronic effects; yields are limited by the competing decomposition of 1 to acetol; Q2 trapping of free-radical intermediates is observed. Dioxiranes, three-membered cyclic peroxides, are of interest (in part) because of high reactivity in oxygen-atom transfer chemistry.' Based on kinetics, stereochemical and labeling data, Edwards and Curci concluded2 that dimethyldioxirane was the active oxygen-atom transfer species in the peroxymonosulfate (oxone)/acetone system. Recent work3 has shown that dioxiranes are isolable by low-temperature distillation. Characterization of dioxiranes has been accomplished3-5 by physical and spectroscopic methods. Dimethyldioxirane 1 has been shown to be useful for the oxidation of many classes of organic compounds1 We have investigated6 the mechanism of epoxidation by 1. Oxygen-atOm insertion reactions into C-H bonds by dioxirane 1 have been reported. 7 The Baeyer-Villiger type oxidation of acetaldehyde3 by