Abstract
AbstractAlcoholic solvents, especially methanol, show an activating affect for heteropolyacids in homogenously catalysed glucose transformation reactions. In detail, they manipulate the polyoxometalate‐based catalyst in a way that thermodynamically favoured total oxidation to CO2 can be completely supressed. This allows a nearly 100 % carbon efficiency in the transformation reaction of glucose to methyl formate in methanolic solution at mild reaction conditions of 90 °C and 20 bar oxygen pressure. By using powerful spectroscopic tools like 51V‐NMR and continuous wave EPR we could unambiguously prove that the vanadate‐methanol‐complex[VO(OMe)3]n is responsible for the selectivity shift in methanolic solution compared to the aqueous reference system.
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