Stereoretentive transformation of biomass hexoses into optically pure glyceric acid at near‐ambient temperature

The synthesis of chiral C 3 acids from hexoses remains a formidable challenge due to the formed racemic intermediates. We here present an innovative strategy employing Ag/ZrO₂ catalyst combined with base promoter, achieving L‐sorbose transformation selectively toward L‐glyceric acid at near‐ambient temperature (40°C). The precise C3–C4 cleavage partitions C4–C6 backbone into a chiral intermediate (L‐glyceraldehyde), while C1–C3 segment to achiral dihydroxyacetone. Ag/ZrO₂–base synergies steer the rapid oxidation of chiral intermediate to L‐glyceric acid with perfect chirality retention at C5, and concurrently channels the achiral dihydroxyacetone toward deep degradation into shorter acids. This dual transformation not only suppresses the deleterious glyceraldehyde‐dihydroxyacetone tautomerism but also avoids racemization. A remarkable L‐glyceric acid yield (88.1%) with >99% ee is achieved, and the feedstock can be extended to D‐sorbose and other hexoses. This work overcomes a long‐standing enantioselectivity dilemma in the synthesis of chiral glyceric acid from broader hexoses.