7.24 Oxidation of Carbon–Halogen Bonds

Abstract

Oxidation of relatively inactive substrate, such as methyl arenes or alkyl carbonyl compounds, to aldehydes or ketones is difficult and requires strong oxidant and harsh reaction conditions. Thus, successive halogenation to halides and oxidation of halides are complementary and reliable methods to obtain the relatively inaccessible carbonyl compounds from lower oxidation substrates. Halides can be oxidized to carbonyl compounds using milder oxidant such as sulfoxide, 2-nitropropane, N-oxide, nitrate, hexamethylenetetramine, metal oxide, and halogen compound. Furthermore, hydrogen peroxide and molecular oxygen have been used as stoichiometric oxidants. This review provides guidelines for the oxidation of halides to carbonyl compounds, which include the substrate scope and limitations, recent application for the synthesis of various organic compounds, and mechanism.