Metal-Catalyzed Baeyer-Villiger Oxidations

The Baeyer-Villiger oxidation of ketones (BV) is a century-old organic reaction for the conversion of ketones into the corresponding esters or lactones using, for example, an organic peroxyacid as a stoichiometric oxidant. The practical use of the BV reaction on cyclobutanones is mainly related to its asymmetric version. This chapter shows some examples of possible target molecules, all achievable via BV oxidation of simple substituted four-, five-, and six-membered ring ketones. The efficient oxidation of ketones other than cyclobutanones has been achieved only with (CH3)ReO3, with a class of silicotungstate polyoxometalates, and with a series of diphosphine Pt(II) complexes, all working with hydrogen peroxide as the terminal oxidant. The platinum system still represents the most versatile class of catalysts for the BV reaction in terms of ligand tuning, choice of possible solvents, and the possibility to be used in enantioselective transformations.