ChemSusChem · 2015 · 38 citations · 37 references
Natural SciencesBiochemistryChemistryBiocatalysisCarbohydrate ChemistryCatalysisBiocatalytic GlycosylationCarbohydrate SynthesisCatalytic MechanismsEnzymatic CatalysisGlycan BiosynthesisGlycosidic Bond HydrolysisCarbohydrate EpimerizationComplex OxidesGlycan EpimerizationLayered Transition Metal OxidesMixed Metal OxidesMolybdenum SulfidesStructured Catalysts
Both non-acidic LiNbMoO6 and strongly acidic HNbMoO6 efficiently catalyze the epimerization of sugars including glucose, mannose, xylose, and arabinose in water. The reactions over these oxides reached almost equilibrium within a few hours where yields of corresponding epimers from glucose, xylose, and arabinose were 24-29%. The layered mixed oxides functioned as heterogeneous catalysts and could be reused without loss of activity, whereas bulk molybdenum oxide MoO3 was completely dissolved during the reaction. A (13)C substitution experiment showed that the reaction proceeds through a 1,2-rearrangement mechanism. The surface Mo octahedra were responsible for the activity. The layered HNbMoO6 could also afford mannose from cellobiose through hydrolysis and successive epimerization.
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