α-Deuterated amino acids hold exceptional significance in chemistry, biology, and medicine. Consequently, the development of highly efficient synthetic methodologies for their preparation has long been a central objective in synthetic chemistry. Over the past several decades, catalytic asymmetric deuteration of unsaturated bonds—particularly C=C and C=N—and catalytic asymmetric α-H/D exchange of readily accessible amino acid derivatives have emerged as the predominant strategies. In contrast, the catalytic asymmetric α-functionalization of α-deuterated glycine derivatives has received comparatively limited attention from the chemical community, despite its initial disclosure as early as 2002. In principle, this approach represents a highly promising route to chiral α-deuterated amino acids, owing to its broad functional group compatibility and versatility with diverse electrophilic reagents. Indeed, numerous catalytic asymmetric α-functionalization reactions of glycine derivatives have been successfully developed in recent years, laying a solid foundation for extending such transformations to α-deuterated substrates. Nevertheless, corresponding catalytic asymmetric methodologies remain scarce. Building upon our prior work on asymmetric α-functionalization of amino acid derivatives enabled by synergistic chiral aldehyde/palladium dual catalysis, we aim to revitalize research efforts toward the discovery of novel α-functionalization reactions of α-deuterated glycine derivatives. In this work, we employ NH₂-unprotected α-deuterated glycine esters and allylic alcohol derivatives as substrates, and a combining system comprising a chiral aldehyde, a palladium-phosphine complex and zinc chloride, as the synergistic catalyst. The reaction is conducted in toluene under a nitrogen atmosphere at ambient temperature for 10 hours, using DABCO as the base. This protocol affords a series of α-functionalized, α-deuterated amino acid derivatives in good yields, with high enantioselectivities and excellent deuterium retention. Through simple derivatization of the catalytic products, the construction of α-deuterated aspartic acid, asparagine, lysine, and arginine derivatives was successfully achieved. This work provides a good example for the preparation of α-deuterated α-amino acid esters in a step-economic manner.