Unveiling the mechanism for selective cleavage of C-C bonds in sugar reactions on tungsten trioxide–based catalysts

Conversion of naturally occurring sugars, the most abundant biomass resources on Earth, to fuels and chemicals provides a sustainable and carbon-neutral alternative to the current fossil resource–based processes. Tungsten-based catalysts (e.g., WO(3)) are efficient for selectively cleaving C-C bonds of sugars to C(2,3) oxygenate intermediates (e.g., glycolaldehyde) that can serve as platform molecules with high viability and versatility in the synthesis of various chemicals. Such C-C bond cleavage follows a mechanism distinct from the classical retro-aldol condensation. Kinetic, isotope (13)C-labeling, and spectroscopic studies and theoretical calculations, reveal that the reaction proceeds via a surface tridentate complex as the critical intermediate on WO(3), formed by chelating both α- and β-hydroxyls of sugars, together with the carbonyl group, with two adjacent tungsten atoms (W-O-W) contributing to the β-C-C bond cleavage. This mechanism provides insights into sugar chemistry and enables the rational design of catalytic sites and reaction pathways toward the efficient utilization of sugar-based feedstocks.