Facile thiolation of hydroxyl functional polymers

Sulfur is an important component in many biological systems. In the hands of an organic chemist it can provide an ample handle for a myriad of robust reactions including thiol–ene click chemistry. However, in polymer chemistry the thiol functionality is rarely attributed to the macromolecule due to unatainable synthetic protocols. Herein, we provide a simple and robust strategy to produce thiol-functional polymers. The chemistry capitalizes on an unsymmetrical disulfide that straightforwardly converts hydroxyl functional polymers to their thiolated counterpart. Finally, PEG hydrogels, using both thiol–ene and Michael addition, is used to showcase the possibilities presented by thiol functional polymers.