Vanadium complexes have proven to be effective catalysts for the activation of peroxides and the selective oxidation of substrates like bromides, sulfides and alkenes. Besides their capability to form metalloperoxo species, which effectively transfer oxygen atoms to the substrate, these systems are synthetically useful for obtaining valuable oxidized molecules on a preparative scale, with a high degree of selectivity and TONs. Furthermore, the use of environmentally friendly oxidants like hydrogen and alkyl hydroperoxides increases significantly their potential application at an industrial level.
Here we report a critical survey on the most effective homogeneous vanadium catalysts reported in the last decade concerning their synthetic application in oxygen transfer reactions (sulfoxidation, epoxidation, haloperoxidation) using hydrogen peroxide or alkyl hydroperoxides, demonstrating the different classes of ligands and complexes, their catalytic performances, their reactivity, chemo, stereo and substrate selectivity. Some examples of the use of non conventional reaction media or techniques and catalyst recycling studies will be also discussed.