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We discovered that highly regioselective H/D exchange can be achieved on the α‐position of the pentafluorophenyl (Pfp) ester using Et3N as the catalyst and D2O as the deuterium source. Our computational and experimental results showed that the Pfp group can significantly increase the acidity of the α‐hydrogen of the ester. This mild reaction condition tolerated a variety of functional groups. 90%∼98% yields and 91%∼98% deuterium incorporations were obtained with all the tested Pfp esters. Taking advantage of the high reactivity of Pfp esters, a series of valuable α‐deuterio carboxylic acid derivatives, including herbicide, drugs and drug intermediates, have been synthesized using α‐deuterio Pfp esters as precursors. [ABSTRACT FROM AUTHOR]

Deuterated polymers have wide applications but limited synthetic methods. In this study, we report an efficient two-step approach for the synthesis of deuterated polyesters and polyurethanes. Firstly, two practical single-electron transfer (SET) reductive-deuteration methods have been developed for site-selective introduction of C(sp3)–D into diol monomers. Nine deuterated diol monomers with high deuterium incorporations were synthesized under SmI2 –D2 O and/or Na-EtOD- d 1 SET reductive-deuteration conditions. Then, six typical deuterated polyesters and polyurethanes were synthesized using those deuterated monomers under typical polymerization conditions. In all the synthesized polymers, high deuterium incorporation was fully maintained, which showcased the potential application of this approach for the synthesis of polymers with site-specific deuterium labelling. [ABSTRACT FROM AUTHOR]