CHAPTER 4: Thiol–Thiosulfonate Chemistry in Polymer Science: Simple Functionalization of Polymers via Disulfide Linkages

Herein we highlight the reaction of thiols with thiosulfonates yielding asymmetric disulfides. The chapter begins with an overview of the synthesis and reactivity of functional thiosulfonates and is followed by a review of polymeric thiosulfonates. We then emphasize the novel use of thiosulfonates as trapping/functionalization agents for macromolecular thiols obtained from parent (co)polymers prepared by reversible addition‐fragmentation chain transfer (RAFT) radical polymerization. We also note how such facile disulfide‐forming chemistries can be readily employed simultaneously with other highly efficient coupling chemistries with an emphasis on the concurrent reaction of activated esters with amines in the presence of thiosulfonates. Finally, we discuss the use of methyl disulfide (SSMe) functional/end‐modified (co)polymers as reagents for the formation of polymeric self‐assembled monolayers (polymer brushes) on metal surfaces such as nanoparticles and quantum dots.