Mechanism of glucose isomerization using a solid Lewis acid catalyst in water.

^1H and ^(13)C NMR spectroscopy on isotopically labeled glucose reveals that in the presence of tin-containing zeolite Sn-Beta, the isomerization reaction of glucose in water proceeds by way of an intramolecular hydride shift (see scheme) rather than proton transfer. This is the first mechanistic demonstration of Sn-Beta acting as a Lewis acid in a purely aqueous environment.

[1]  A. Corma,et al.  Water Resistant, Catalytically Active Nb and Ta Isolated Lewis Acid Sites, Homogeneously Distributed by Direct Synthesis in a Beta Zeolite , 2009 .

[2]  I. A. Rose,et al.  Anomeric specificity and mechanism of two pentose isomerases. , 1971, Biochemistry.

[3]  A. Corma,et al.  Sn-Beta zeolite as diastereoselective water-resistant heterogeneous Lewis-acid catalyst for carbon-carbon bond formation in the intramolecular carbonyl-ene reaction. , 2004, Chemical communications.

[4]  A. Corma,et al.  Water-resistant solid Lewis acid catalysts: Meerwein–Ponndorf–Verley and Oppenauer reactions catalyzed by tin-beta zeolite , 2003 .

[5]  H. L. Carrell,et al.  Metal ion roles and the movement of hydrogen during reaction catalyzed by D-xylose isomerase: a joint x-ray and neutron diffraction study. , 2010, Structure.

[6]  David Neuhaus,et al.  The Nuclear Overhauser Effect in Structural and Conformational Analysis , 1989 .

[7]  B. Yang,et al.  Alkaline degradation of glucose: effect of initial concentration of reactants , 1996 .

[8]  S. Saravanamurugan,et al.  Conversion of Sugars to Lactic Acid Derivatives Using Heterogeneous Zeotype Catalysts , 2010, Science.

[9]  A. Corma,et al.  Determination of the catalytically active oxidation Lewis acid sites in Sn-beta zeolites, and their optimisation by the combination of theoretical and experimental studies , 2005 .

[10]  R. Rosenfeld Nature , 2009, Otolaryngology--head and neck surgery : official journal of American Academy of Otolaryngology-Head and Neck Surgery.

[11]  Jianmin Xiong,et al.  Zeolite-catalyzed isomerization of triose sugars. , 2009, ChemSusChem.

[12]  M. Rao,et al.  Molecular and industrial aspects of glucose isomerase. , 1996, Microbiological reviews.

[13]  R. W. Nagorski,et al.  Mechanistic imperatives for aldose-ketose isomerization in water: specific, general base- and metal ion-catalyzed isomerization of glyceraldehyde with proton and hydride transfer. , 2001, Journal of the American Chemical Society.

[14]  Karen N. Allen,et al.  Isotopic exchange plus substrate and inhibition kinetics of D-xylose isomerase do not support a proton-transfer mechanism. , 1994, Biochemistry.

[15]  A. Corma,et al.  Al-free Sn-Beta zeolite as a catalyst for the selective reduction of carbonyl compounds (Meerwein-Ponndorf-Verley reaction). , 2002, Journal of the American Chemical Society.

[16]  Juben Nemchand Chheda,et al.  Katalytische Flüssigphasenumwandlung oxygenierter Kohlenwasserstoffe aus Biomasse zu Treibstoffen und Rohstoffen für die Chemiewirtschaft , 2007 .

[17]  A. Corma,et al.  Sn-zeolite beta as a heterogeneous chemoselective catalyst for Baeyer–Villiger oxidations , 2001, Nature.

[18]  I. A. Rose,et al.  Stereochemical evidence for a cis-enediol intermediate in Mn-dependent aldose isomerases. , 1969, Biochimica et biophysica acta.

[19]  A. Corma,et al.  Lewis acids as catalysts in oxidation reactions: from homogeneous to heterogeneous systems. , 2002, Chemical reviews.

[20]  A. Corma,et al.  Mechanism of the Meerwein-Ponndorf-Verley-Oppenauer (MPVO) redox equilibrium on Sn- and Zr-beta zeolite catalysts. , 2006, The journal of physical chemistry. B.

[21]  Yuriy Román‐Leshkov,et al.  Production of dimethylfuran for liquid fuels from biomass-derived carbohydrates , 2007, Nature.

[22]  G. Huber,et al.  Liquid-phase catalytic processing of biomass-derived oxygenated hydrocarbons to fuels and chemicals. , 2007, Angewandte Chemie.

[23]  H. V. Bekkum,et al.  Enolisation and isomerisation of monosaccharides in aqueous, alkaline solution , 1979 .

[24]  F. Young Biochemistry , 1955, The Indian Medical Gazette.

[25]  Manuel Moliner,et al.  Tin-containing zeolites are highly active catalysts for the isomerization of glucose in water , 2010, Proceedings of the National Academy of Sciences.