Organoselenium Compounds as Glutathione Peroxidase Mimetics and Catalysts for Synthetically Useful Oxidation Reactions

Organoselenium compounds are efficient and versatile catalysts for the reduction of hydroperoxides with thiols and the oxidation of a variety of substrates with peroxides. Previously, the Back group has reported the remarkable catalytic activity of cyclic seleninate esters and spirodioxyselenuranes for the reduction of peroxides. These small-molecule selenium compounds were designed to function as mimetics of the selenoenzyme GPx, which plays a vital role in protecting organisms from oxidative stress. This thesis describes an investigation into the substituent effects for the above classes of selenium-containing compounds. Additionally, these species were shown to be effective catalysts for the hydrogen peroxide oxidation of sulfides, alkenes and enamines to sulfoxides, epoxides and α-hydroxy ketones, respectively. Attempts were also made at enantioselective variations of these processes by means of novel chiral selenium catalysts. However, useful levels of chirality transfer have yet to be achieved.