Selenium‐Promoted Oxidation of Organic Compounds: Reactions and Mechanisms

Abstract

AbstractOxidation reactions are fundamental processes widely applied in organic synthesis. Elemental selenium and more often its compounds have been successfully used as stoichiometric reagents and catalysts for oxidation of different organic substrates. Selenium(IV) oxide, areneseleninic acids and their anhydrides are widely used as stoichiometric oxidants or as oxygen‐transfer agents for oxygen donors, particularly hydrogen peroxide and tert‐butyl hydroperoxide. Organic diselenides (the precursors of seleninic acids) have been used as oxidation catalysts while dimethyl and diphenyl selenoxides are stoichiometric oxidants. Selenenamides, such as 2‐phenyl‐1,2‐benzisoselenazol‐3(2H)‐one (ebselen) and its analogues, known as glutathione peroxidase mimics acting via active hydroperoxide intermediates, are efficient and selective oxidation catalysts. Selenium(IV) oxide and some organoselenium compounds have been successfully applied for various oxidations useful in practical organic syntheses such as epoxidation, 1,2‐dihydroxylation, and α‐oxyfunctionalization of alkenes as well as for ring contraction of cycloalkanones, conversion of halomethyl, hydroxymethyl, or active methylene groups into formyl groups, oxidation of aldehydes into carboxylic acids, sulfides into sulfoxides, and secondary amines into nitrones, regeneration of parent carbonyl compounds from their azomethine derivatives and for other reactions. The oxidation mechanisms depend on the substrate and oxidant or catalyst used. The electrophilic center localized on the selenium atom or the nucleophilic center localized on the oxygen atom of the selenahydroperoxide group are involved in the reaction mechanism. In both cases the selenium‐containing moiety is a good leaving group. Exceptionally oxidation can proceed via free radical selenium species. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)