Molecular Conversion of Photooxidation of Single Bond

光敏化氧化(单线态氧氧化)是已知的一种富含电子的烯烃，可提供相应的过氧化物系。然而，单键的光氧化作用尚未见报道。在这个项目中，我们开发了一种新型的单线态氧与单键的反应。二硅氧烷和草二硅烷的单线态氧氧化生成了相应的环状过氧化物，这是一类新的环状过氧化物类的衍生物。通过捕集实验、初始生成的过氧化中间体的理论研究和立体化学研究，阐明了反应机理。环丙烷单次氧氧化得到相应的二氧杂环戊烷，首次证明了氧插入碳-碳单键。并对反应机理进行了探讨。

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.