Mechanistic aspects of vanadium catalysed oxidations with peroxides

The enhancement of the reactivity of peroxides, particularly hydrogen peroxide and alkylhydroperoxides, in the presence of vanadium catalysis is a very well known process. The catalytic effect is determined by the formation of an intermediate whose nature depends on the peroxides used and on its interaction with the metal precursor, high-valent peroxo vanadium species being usually the reactive oxidants. During the last decades the mechanistic details for several types of oxidation reactions have been elucidated. Interestingly, in a number of cases theoretical calculations offered support to the proposed reaction pathways. In general, V(V) peroxo species behave as electrophilic oxygen transfer reagents thus reacting preferentially with the more nucleophilic functional group present in the molecule. In several instances the chemoselectivity observed in such processes is very high when not absolute. As far as vanadium peroxides are concerned, a radical oxidative reactivity toward alkanes and aromatics has been also observed; also for this latter chemistry, diverse research groups studied in detail the mechanism. On the other hand, no clear-cut evidence of nucleophilic reactivity of vanadium peroxo complexes has been obtained. Here we collect a selection of recent achievements concerning the reaction mechanisms in the vanadium catalysed oxidation and bromination reactions with peroxides.