title: A one-pot synthesis of 1,6,9,13-tetraoxadispiro(4.2.4.2)tetradecane by hydrodeoxygenation of xylose using a palladium catalyst.
abstract: In an effort to expand the number of biobased chemicals available from sugars, xylose has been converted to 1,6,9,13-tetraoxadispiro(4.2.4.2)tetradecane 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. (1)H and (13)C 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.
authors.affiliation: United States Department of Agriculture, Agricultural Research Service, National Center for Agricultural Utilization Research, Renewable Products Technology Research, 815 N. University, St. Peoria, IL 61604, United States. Electronic address: michael.jackson@ars.usda.gov.
authors.forename: Michael A
authors.initials: MA
authors.lastname: Jackson
authors.affiliation: United States Department of Agriculture, Agricultural Research Service, National Center for Agricultural Utilization Research, Renewable Products Technology Research, 815 N. University, St. Peoria, IL 61604, United States.
authors.forename: Judith A
authors.initials: JA
authors.lastname: Blackburn
authors.affiliation: United States Department of Agriculture, Agricultural Research Service, National Center for Agricultural Utilization Research, Renewable Products Technology Research, 815 N. University, St. Peoria, IL 61604, United States.
authors.forename: Neil P J
authors.initials: NP
authors.lastname: Price
authors.affiliation: United States Department of Agriculture, Agricultural Research Service, National Center for Agricultural Utilization Research, Functional Foods Research, 815 N. University, St. Peoria, IL 61604, United States.
authors.forename: Karl E
authors.initials: KE
authors.lastname: Vermillion
authors.affiliation: United States Department of Agriculture, Agricultural Research Service, National Center for Agricultural Utilization Research, Plant Polymer Research, 1815 N. University, St. Peoria, IL 61604, United States.
authors.forename: Steven C
authors.initials: SC
authors.lastname: Peterson
authors.affiliation: Department of Chemistry, Illinois State University, Normal, IL 61790, United States.
authors.forename: Gregory M
authors.initials: GM
authors.lastname: Ferrence
mesh_terms: D000473:Alkanes / Q000138:chemical synthesis* / Q000737:chemistry; D000538:Aluminum Silicates / Q000737:chemistry; D002384:Catalysis; D018360:Crystallography, X-Ray; D009682:Magnetic Resonance Spectroscopy; D015394:Molecular Structure; D010165:Palladium / Q000737:chemistry*; D014994:Xylose / Q000737:chemistry*
chemical_list: D000473:Alkanes; D000538:Aluminum Silicates; D010165:Palladium; D014994:Xylose
keywords: 1,6,9,13-tetraoxadispiro(4.2.4.2)tetradecane; 11β-hydroxysteroid dehydrogenase 1; Arabinose; Pd/silica-alumina; Polymorph; Xylose