5.1 Asymmetric Baeyer–Villiger Oxidation

Abstract

The asymmetric Baeyer–Villiger (B–V) oxidation of cyclic ketones is a useful oxidation reaction in organic synthesis that allows one-step production of chiral lactones by introducing an oxygen atom at the α-position of the carbonyl group. Asymmetric B–V oxidation using enzymatic catalysts, called Baeyer–Villiger monooxygenases (BVMOs), has achieved high enantioselectivity for a wide range of substrates, whereas asymmetric B–V oxidation using nonenzymatic catalysts was not reported until 1994. High enantioselectivity was difficult to achieve in early studies of nonenzymatic B–V oxidation, but has now been achieved through the development of a variety of catalysts in different studies. This chapter reviews previously reported cases of nonenzymatic B–V oxidation, classifying them in accordance with reaction and catalyst type.