TheBaeyer–VilligerOxidation of Ketones and Aldehydes

Abstract The oxidative conversion of alicyclic ketones into lactones with permonosulfuric acid was discovered by Baeyer and Villiger in 1899, and in their honor the general process by which ketones are converted into esters or lactones is now known as the Baeyer–Villiger reaction. The literature on this synthetically useful process has been reviewed comprehensively through 1953 in Volume 9 of Organic Reactions , and less comprehensive reviews of the reaction have appeared since then. More recent investigations have led to the development of new synthetic reagents, to improvements in experimental reaction conditions, and to a better understanding of regiochemical and stereochemical aspects of the reaction. Baeyer–Villiger reactions now often can be carried out with functional group chemoselectivity and regiochemical control. Although the recent removal from commerce of 90% hydrogen peroxide and reagents based upon this oxidant are a setback to Baeyer–Villiger reaction methodology, alternative reagents, catalysts, and methods described in this review are available to fill the gaps. The definition of the Baeyer–Villiger reaction is somewhat fuzzy, and can be considered to include both ketones and aldehydes. In addition to the traditional use of organic and inorganic peracids as oxidants, examples of oxygen insertion reactions using hydrogen peroxide, alkyl peroxides, and several metal ion oxidants are considered to fall within the scope of this chapter and are included in the tabular survey.