The Peroxyester Reaction

Abstract

Abstract The reactions of t‐butyl peroxyesters with various classes of compounds in the presence of a catalytic amount of copper ions produce well‐defined acyloxy derivatives. This peroxyester reaction, discovered by Kharasch and Sosnovsky, can be used to effect one‐step oxidation of saturated and unsaturated hydrocarbons, alcohols, aldehydes, esters, ethers, sulfides, organosilicon compounds, etc. The reaction can be highly selective: in most cases only one specific carbon atom is attacked. However, with some ethers and, sulfides the reaction can take a more complex course, other products being formed in addition to the acyloxy derivatives. The mechanism of the reaction has been extensively investigated, and several concerted and chain mechanisms have been proposed.