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A one-pot synthesis of 1,6,9,13-tetraoxadispiro( by hydrodeoxygenation of xylose using a palladium catalyst

Michael A. Jackson, Judith A. Blackburn, Neil P.J. Price, Karl E. Vermillion, Steven C. Peterson, Gregory M. Ferrence
Carbohydrate research 2016 v.432 pp. 9-16
X-ray diffraction, catalysts, chromatography, data collection, esterification, hydrogen, mammals, palladium, phase transition, phosphates, temperature, xylose
In an effort to expand the number of biobased chemicals available from sugars, xylose has been converted to 1,6,9,13-tetraoxadispiro( in a one-pot reaction using palladium supported on silica-alumina as the catalyst. The title compound is produced in 35–40% yield under 7 MPa H2 pressure at 733 K using 3–10 wt%Pd on silica-alumina catalyst. It is isolated using a combination of liquid-liquid extractions and flash chromatography. This dimer can be converted to its monomer, 2-hydroxy-(2-hydroxymethyl)tetrahydrofuran, which ring opens under acid conditions to 1,5-dihydroxy-2-pentanone. This diol can then be esterified with vinylacetate in phosphate buffer to produce 1,5-bis(acetyloxy)-2-pentanone which is an inhibitor of mammalian 11β-hydroxysteroid dehydrogenase 1. 1H and 13C nmr spectra of each of these species are reported. The single crystal X-ray structure of the title compound is also reported. These data were collected in a temperature range of 100 K–273 K and show a solid state phase change from triclinic to monoclinic between 175 K and 220 K without a conformational change.