Chemo- and stereoselective CH oxidations and epoxidations/cis-dihydroxylations with H2O2, catalyzed by non-heme iron and manganese complexes

The discovery of simple and efficient catalyst systems for the selective oxofunctionalization of hydrocarbons is a challenging task of modern chemistry. The biomimetic approach, which aims at mimicking the reactivity of natural enzymes in catalyzed transformation with synthetic low-molecular weight compounds, has been widely applied to the search for new transition metal based catalyst systems in the last two decades. In effect, numerous iron and manganese complexes modeling the catalytic performance of non-heme metal-containing monooxygenases have been reported and intensively investigated. In this contribution, non-heme iron- and manganese catalyzed selective oxidations of alkanes, as well as chemo- and stereoselective epoxidations and cis-dihydroxylations of alkenes, using H2O2 as the oxygen source, are reviewed, with major focus on the their synthetic potential. Recent experimental investigations of the nature of catalytically active species and mechanisms of their action are summarized.

► Non-heme Fe and Mn systems for catalytic oxidations with H2O2 are overviewed
► Recent insights into the nature of catalytically active species is presented
► Aminopyridine-iron based systems provide synthetic models of natural monooxygenases
► Mn systems demonstrate high potential in chemo- and stereoselective epoxidations.