A new postpolymerization protocol based on the reactivity of α,α-difluoroacetate esters is proposed and rationalized via a combined effort of computational and experimental methods. Reaction systems designed on the basis of computational results are characterized in detail. It is found that aminolysis of polymers featuring α,α-difluoroacetate esters results in a 100% conversion of ester units to α,α-difluoroacetamide derivatives. This indicates that the new activated ester–amine chemistry reported here offers a promising approach to postpolymerization modifications.

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Poly­(ethyl 2,2-difluoro-2-(4-vinylphenoxy)­acetate) (PSt-OCF2CO2Et) was rationally designed as a vinyl polymer featuring α,α-difluoro-α-(aryloxy)­acetate units as activated ester moieties. The aminolysis of PSt-OCF2CO2Et was conducted, resulting in a 100% conversion of ester units to α,α-difluoroacetamide derivatives. This experimental observation showed good agreement with computational analysis at the density functional theory (DFT) level and the DLPNO-CCSD­(T) level of theory. Specifically, the aminolysis of α,α-difluoro-α-(aryloxy)­acetates was computationally compared with that of structurally similar α,α-difluoroacetates, which are known to show aminolysis reactivity. This revealed that the α-etherification of α,α-difluoroacetates is not detrimental to the aminolysis reactivity despite the presence of an electronegative oxygen atom adjacent to the CF2 units. This research provides a computational understanding of α,α-difluoro-α-(aryloxy)­acetates and easy access to new activated ester moieties in polymer chemistry.