Heterogeneous Base‐Catalyzed Conversion of Glycolaldehyde to Aldotetroses: Mechanistic and Kinetic Insight

Recent strides towards greater sustainability in materials and energy production have led to a resurgence the study utilization of carbohydrates. Opposite C6 C5 carbohydrates, C4 carbohydrates (tetroses) are much less accessible from biological sources. A promising approach for is cracking C2 fragments, subsequent combination two fragments tetroses. Here, we show that suitable choice reaction conditions can kinetically stabilize rare aldotetroses threose (THR) erythrose (ERY). The latter yields THR ERY at high selectivity under benign conditions, using commercial resins with tertiary amine groups as catalyst. Isotope incorporation into GA D2O solvent introduced reference probe competitive formation deuterated low-populated, not directly detected enediol intermediate formed rate-determining step. Reaction progress tracked situ by NMR ex chromatography validates overall conversion first order respect due slow initial enolization. Cyclization slows their further thermodynamically more stable erythrulose sugars.