Flavins as organocatalysts for environmentally benign molecular transformations

Abstract

Recent progress in the development of flavin-catalyzed oxidations and related reactions is described with respect to scope, limitation, and reaction mechanism. The 4a-hydroperoxyflavins, which are the most simplified model compounds of flavoenzymes, act as catalytically active species for the oxidation of organic substrates with the help of H(2)O(2) or O(2) as a mild oxidant. This principle behind the simulation of flavoenzymes led to the discovery of a variety of environmentally benign, oxidative transformations of secondary amines to nitrones, tertiary amines to N-oxides, sulfides to sulfoxides, and Baeyer-Villiger oxidations of ketones. Asymmetric oxidation of sulfides can also be performed with several chiral flavin catalysts. One of the fortunate outcomes of this study is the development of an environmentally friendly ("green") method for the "aerobic hydrogenation" of olefins, which is achieved by in situ generation of diimide with the aid of the flavin-catalyzed oxidation of hydrazine under an O(2) atmosphere.