Catalytic oxidations by peroxy, peroxo and oxo metal complexes: an interdisciplinary account with a personal view

In this account, we present a brief overview of our interdisciplinary efforts on the metal-assisted selective oxyfunctionalization of organic substrates in the ‘Sonderforschungsbereich (SFB 347): Selektive Reaktionen Metall-aktivierter Moleküle’. The reactivity and selectivity of peroxy-, peroxo-, and oxo-type metal oxidants have been studied to gain insight into the mechanism of the oxygen transfer by such catalytic oxidants. Based on our mechanistic work, effective catalytic oxyfunctionalization methods have been developed by employing Ti, V, Re, Mn or Cr complexes as catalysts for the chemo-, regio-, diastereo- and enantioselective synthesis of hydroxy epoxides (from olefins), sulfoxides (from sulfides), and silanols (from silanes). We show that the stoichiometric dimethyldioxirane (DMD) oxidation of ligands in selected transition-metal complexes provides an useful tool for the synthesis of oxyfunctionalized compounds.