A one-pot synthesis of 1,6,9,13-tetraoxadispiro(4.2.4.2)tetradecane by hydrodeoxygenation of xylose using a palladium catalyst

Authors: Jackson, Michael - Mike; Blackburn, Judith; Price, Neil; Vermillion, Karl; Peterson, Steven - Steve; FERRENCE, GREGORY - Illinois State University

Submitted to: Carbohydrate Research
Publication Type: Peer Reviewed Journal
Publication Acceptance Date: 6/9/2016
Publication Date: 6/14/2016
Publication URL: https://handle.nal.usda.gov/10113/5287219
Citation: Jackson, M.A., Blackburn, J.A., Price, N.P.J., Vermillion, K.E., Peterson, S.C., Ferrence, G.M. 2016. A one-pot synthesis of 1,6,9,13-tetraoxadispiro(4.2.4.2)tetradecane by hydrodeoxygenation of xylose using a palladium catalyst. Carbohydrate Research. 432:9-16. doi: 10.1016/j.carres.2016.06.003.

Interpretive Summary: In this work, we have demonstrated that the common sugar xylose can be converted to a series of useful compounds. One of these, 1,6,9,13-tetraoxadispiro(4.2.4.2)tetradecane, has a fragrance that is described as being similar to hazelnuts or bourbon. We subsuquently converted this product to a compound that inhibits an enzyme known to exacerbate a host of health problems associated with a variety of metabolic disorders including hypertension, obesity, and insulin resistant diabetes. This project was initially undertaken to explore routes to industrially useful chemicals from agricultural wastes that included xylose.

Technical 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 160°C using 3-10wt%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 11ß-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 100K to 273K and show a solid state phase change from triclinic to monoclinic between 175K and 220K without a conformational change.