1991 Fiscal Year Final Research Report Summary

Molecular Conversion of Photooxidation of Single Bond

Research Project

Project/Area Number	02640378
Research Category	Grant-in-Aid for General Scientific Research (C)
Allocation Type	Single-year Grants
Research Field	有機化学一般
Research Institution	University of Tsukuba
Principal Investigator	AKASAKA Takeshi University of Tsukuba Department of Chemistry Associate Professor, 化学系, 助教授 (60089810)
Project Period (FY)	1990 – 1991
Keywords	singlet oxygen / photooxidation / photosensitized oxygenation / cyclopropane / disilirane / dioxolane / disiladioxolane / active oxygen species
Research Abstract	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.

(6 results)