Selective Oxidation – Homogeneous

Abstract

In the manufacture of fine chemicals there is a considerable pressure to replace traditional oxidation techniques, using stoichiometric quantities of high valent metal salts, with cleaner, catalytic alternatives. This article focuses on homogeneous catalysis of liquid‐phase oxidations employing dioxygen, hydrogen peroxide, or alkyl hydroperoxides as the primary oxidant. Where relevant, heterogeneous equivalents are also discussed. Following a general introduction, which includes a discussion of the different reaction mechanisms and of the design of ligands for oxidation catalysts, the different classes of substrates are discussed. These are alkenes (epoxidation, vicinal dihydroxylation, oxidative cleavage, ketonization, and allylic oxidation), alkanes and alkyl aromatics (side‐chain versus aromatic‐ring oxidation), oxygen‐containing compounds (alcohols, diols, aldehydes, ketones, phenols, and ethers), amines, and sulfur‐containing compounds. A separate section is devoted to asymmetric catalysis (epoxidation and dihydroxylation of olefins, sulfoxidation, and Baeyer–Villiger oxidation).