Enhanced Ribose‐Forming Pathways in the Formose Reaction by Oxometalate Catalysts

Controlling product selectivity in complex chemical reaction networks (CRNs) remains a major challenge in rational catalyst design, as multiple competing pathways often yield diverse products. The formose reaction, an autocatalytic process that converts formaldehyde (HCHO) into monosaccharides, represents a prototypical nonenzymatic CRN. It has long been investigated in the context of prebiotic chemistry and, more recently, as a system that transforms a C1 compound into higher‐carbon species. In this study, we examined the influence of catalysts on pathway selectivity within this reaction network. Sodium tungstate (Na 2 WO 4 ), which we have previously investigated, produces a product distribution distinct from that obtained with conventional strong base catalysts. Analysis of the aldopentose (C5a) formation pathway revealed that xylose formation predominates under NaOH catalysis, whereas Na 2 WO 4 selectively promotes ribose production. Mechanistic experimental studies and density functional theory (DFT) calculations indicate that WO 4 2− preferentially stabilizes the transition state leading to ribose. These findings demonstrate that understanding catalyst–substrate interactions and identifying the reaction pathways they govern in the formose reaction network enables the prediction of product distributions in complex CRNs.