Thiol-epoxy ‘click’ reaction in polymer synthesis

The base-catalyzed ring-opening reaction of epoxides by thiol nucleophiles, commonly known as the thiol-epoxy ‘click’ reaction, is a versatile method for forming thioether bonds. This review offers mechanistic insights into the reaction and explores its applications in polymer synthesis. The discussion also includes post-polymerization modifications of thioether linkages into sulfoxides, sulfones, and cationic sulfonium salts, as well as esterification of the secondary hydroxyl groups generated by the ‘click’ reaction. Additional topics include scalability, chemoselectivity, regioselectivity, and the formation of disulfide defects. Practical recommendations are provided for optimizing reaction conditions and minimizing side reactions. Finally, future directions are proposed to further expand the utility of this reaction in polymer chemistry.