Molecular Conversion of Photooxidation of Single Bond

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The Photosensitized oxygenation(singlet oxygen oxidation)a variety of eletron rich olefins is known to afford the corresponding peroxides. However, none of photooxygenation of single bonds has been reported. In this project, we have developed a new type of reaction of singlet oxygen with single bonds.Singlet oxygen oxidation of disilirajles and oxadisiliranes afforded the corresponding cyclic peroxides, derivatives of a novel class of cyclic peroxides. The reaction mechanism was elucidated by means of the results derived from trapping experiments, theoretical studies of the initially formed peroxidic intermediate, and stereochemical investigation.Singlet oxygen oxidation of tetraanisylcylopropane gave the corresponding dioxolane quantitatively, demonstrating a first example of dioxygen insertion into a carbon-carbon single bond. The reaction mechanism was also discussed.