Metalloporphyrin-based oxidation systems: From biomimetic reactions to application in organic synthesis

Abstract

The oxidation of organic substrates catalyzed by metalloporphyrins constitutes a major class of biomimetic oxidation reactions used in modern synthetic chemistry. Ruthenium porphyrins are among the most extensively studied metalloporphyrin oxidation catalysts. This article provides a brief outline of the metalloporphyrin-based oxidation systems and is focused on the oxidation reactions catalyzed by ruthenium porphyrins performed in the author's laboratory. A series of ruthenium porphyrin catalysts, including those immobilized onto insoluble supports and covalently attached to soluble supports, promote the oxidation of a wide variety of organic substrates such as styrenes, cycloalkenes, α,β-unsaturated ketones, steroids, benzylic hydrocarbons and arenes with 2,6-dichloropyridine-N-oxide or air in up to >99% yields, with high regio-, chemo- and/or stereoselectivity, and with product turnovers of up to 3.0 × 104, demonstrating the potential application of ruthenium porphyrin-based oxidation systems in organic syntheses. © 2009 The Royal Society of Chemistry.