Photocontrolled Radical Polymerization from Hydridic C–H Bonds

Given the ubiquity of carbon-hydrogen bonds in biomolecules and polymer backbones, the development of a photocontrolled polymerization selectively grafting from a C-H bond represents a powerful strategy for polymer conjugation. This approach would circumvent the need for complex synthetic pathways currently used to introduce functionality at a polymer chain end. On this basis, we developed a hydrogen-atom abstraction strategy that allows for a controlled polymerization selectively from a hydridic C-H bond using a benzophenone photocatalyst, a trithiocarbonate-derived disulfide, and visible light. We performed the polymerization from a variety of ethers, alkanes, unactivated C-H bonds, and alcohols. Our method lends itself to photocontrol which has important implications for building advanced macromolecular architectures. Finally, we demonstrate that we can graft polymer chains controllably from poly(ethylene glycol) showcasing the potential application of this method for controlled grafting from C-H bonds of commodity polymers.