Mechanism of addition of siglet oxygen to olefins and other substrates

Abstract

Mechanisms of addition of singlet oxygen to various classes of substrates are surveyed. The experimental data for the allylic hydroperoxidation are best fit by a concerted, ‘ene-type’ mechanism; the addition to dienes is probably a Diels-Alder reaction. 1,2-Cycloadditions to electron-rich olefins may proceed by a 1,4-dipolar mechanism, although there is as yet little evidence, while the addition to sulphides may go by a very similar nucleophilic addition to oxygen. © 1971, Walter de Gruyter. All rights reserved.