Biologically inspired non-heme iron-catalysts for asymmetric epoxidation; design principles and perspectives

Abstract

Iron coordination complexes with nitrogen and oxygen donor ligands have long since been known to react with peroxides producing powerful oxidizing species. These compounds can be regarded as simple structural and functional models of the active sites of non-heme iron dependent oxygenases. Research efforts during the last decade have uncovered basic principles and structural coordination chemistry motifs that permit us to control the chemistry that evolves when these iron complexes react with peroxides, in order to provide powerful metal-based, but at the same time selective, oxidising agents. Oxidation methodologies with synthetic value are currently emerging from this approach. The current review focuses on asymmetric epoxidation, a reaction which has large value in synthesis, and where iron/H₂O₂ based methodologies may represent not only a sustainable choice, but may also expand the scope of state-of-the-art oxidation methods. Basic principles that underlay catalyst design as well as H₂O₂ activation are discussed, whilst limitations and future perspectives are also reviewed.