Redox-Mediated and Microwave-Assisted Thiol Activation: Two Approaches to Unsymmetrical Disulfides Synthesis

Abstract

Two approaches to synthesis of unsymmetrical disulfides based on different types of thiol activation, namely, an electrochemical method in the presence of a redox mediator and a microwave irradiation, were discussed. The mediated electrosynthesis procedures were carried out by the oxidative coupling of thiols or by the thiol-disulfide exchange in the presence of redox pairs—substituted o-aminophenol/o-iminobenzoquinone. It has been established that the formation of unsymmetrical disulfides under electrochemical conditions occurs as a result of both the oxidative coupling of sulfur-centered radicals, and a redox-mediator promoted thiol-disulfide exchange, which led to a high yield of heterodimeric products (89%–99%). The microwave-assisted synthesis made it possible to obtain the target products with yields of 13%–86% depending on different irradiation parameters such as power, temperature, and irradiation duration. However, this method requires a rigorous selection of conditions for each reaction and is therefore inferior to the electrochemical approach.