Proton transfer anionic polymerization with C–H bond as dormant species

Abstract Living anionic polymerization is the most common living polymerization with the longest history whereas it generally requires stringent conditions and one metal initiator per polymer chain. Here, we present proton transfer anionic polymerization using acidic C–H bonds as dormant species and base catalysts for methacrylates via reversible chain transfer or termination of the growing enolate species. A weakly acidic compound such as an alkyl isobutyrate serves as the initiator or chain-transfer agent in the presence of a bulky potassium base catalyst to produce a polymer chain and thereby diminish the metal compound per chain ratio. An added alcohol serves as a reversible terminator to tame the propagation. End-functionalized, star, block, and graft polymers are easily accessible from compounds with C–H bonds.