Unveiling α-Etherification Effects on the Aminolysis of α,α-Difluoroacetate Enables the Aminolysis Post-polymerization Modification of α,α-Difluoro-α-(aryloxy)acetate-Containing Polymers

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.