The Alchemy of Fluorine: α,α-Difluoroacetates Unlocking Regenerable Post-Polymerization Modification

Abstract

Post-polymerization modification (PPM) has become a pivotal strategy in modern polymer chemistry, enabling the late-stage functionalization of pre-formed polymer backbones. Among the many reactive motifs employed, fluorinated units have played a central role due to their exceptional electronic properties and chemical robustness. While perfluorinated motifs have traditionally been utilized in polymer materials and PPMs, the exploration of partially fluorinated units remains limited. In this Mini-Review, we highlight recent advances in PPMs in the context of existing methodologies and emphasize the synthetic utility of fluorine-containing units in PPM design. Particular attention is given to α,α-difluoroacetates, a class of partially fluorinated esters that uniquely combine carbonyl activation with α-position masking. The recent integration of α,α-difluoroacetates has enabled efficient aminolysis-based PPMs and, remarkably, has allowed for the regeneration of activated ester polymers. These findings establish the first example of a regenerable aminolysis PPM, marking a conceptual shift toward dynamic and recyclable polymer modifications.