Unravelling the Ru-Catalyzed Hydrogenolysis of Biomass-Based Polyols under Neutral and Acidic Conditions

The aqueous Ru/C‐catalyzed hydrogenolysis of biomass‐based polyols such as erythritol, xylitol, sorbitol, and cellobitol is studied under neutral and acidic conditions. For the first time, the complete product spectrum of C2–C6 polyols is identified and, based on a thorough analysis of the reaction mixtures, a comprehensive reaction mechanism is proposed, which consists of (de)hydrogenation, epimerization, decarbonylation, and deoxygenation reactions. The data reveal that the Ru‐catalyzed deoxygenation reaction is highly selective for the cleavage of terminal hydroxyl groups. Changing from neutral to acidic conditions suppresses decarbonylation, consequently increasing the selectivity towards deoxygenation. Networking for biomass: The Ru/C‐catalyzed hydrogenolysis of biomass‐based polyols such as sorbitol and cellobiose is investigated under neutral and acidic condition. The data reveal a reaction network of (de)hydrogenation, epimerization, decarbonylation, and deoxygenation reactions, for which a comprehensive mechanism is proposed. The addition of acid suppresses decarbonylation, which leads to increased deoxygenation.