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Title: Catalytic production of hexane-1,2,5,6-tetrol from bio-renewable levoglucosanol in water: effect of metal and acid sites on (stereo)-selectivity

Abstract

In this article, we report on a new route to produce hexane-1,2,5,6-tetrol (tetrol) from cellulose-derived levoglucosanol (lgol). We investigate the reaction intermediates formed over metal and acid catalysts, and propose a reaction network for this process. Lgol is converted to tetrol in up to 90% yield over a bifunctional Pt/SiO 2–Al 2O 3 catalyst at 150 °C. High tetrol yields are maintained at lgol concentrations of up to 21 wt% in water. threo- and erythro-lgol first undergo hydrolysis to 3,4-dideoxymannose (DDM) and 3,4-dideoxyglucose (DDG), respectively. This reaction can be carried out selectively over an Amberlyst 70 acid catalyst at a temperature of 100 °C. At a higher temperature of 150 °C with no added catalyst, DDM and DDG undergo aldose–ketose isomerization to 3,4-dideoxyfructose (DDF). DDM is hydrogenated to cis-tetrol over a Pt/SiO 2 catalyst, while DDG is hydrogenated to trans-tetrol. Formation of DDF erases the stereocenter at the C 2 position of lgol, and hydrogenation of DDF produces a nearly 1:1 mixture of cis- and trans-tetrol. Lastly, this catalytic approach to produce tetrol from biomass opens the door to sustainable chemicals derived from tetrol.

Authors:
ORCiD logo [1];  [2];  [1]; ORCiD logo [3];  [1]; ORCiD logo [1]
  1. Univ. of Wisconsin, Madison, WI (United States). Department of Chemical and Biological Engineering
  2. Univ. of Wisconsin, Madison, WI (United States). Department of Chemical and Biological Engineering ; Utrecht University (The Netherlands). Faculty of Science, Debye Institute for Nanomaterials Science
  3. Utrecht University (The Netherlands). Faculty of Science, Debye Institute for Nanomaterials Science
Publication Date:
Research Org.:
Univ. of Wisconsin, Madison, WI (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Bioenergy Technologies Office
Contributing Org.:
University of Wisconsin-Madison Department of Chemistry; University of Wisconsin-Madison School of Pharmacy Analytical Instrumentation Center; Circa Group
OSTI Identifier:
1477860
Alternate Identifier(s):
OSTI ID: 1471254
Grant/Contract Number:  
EE0006878
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Green Chemistry
Additional Journal Information:
Journal Volume: 20; Journal Issue: 19; Journal ID: ISSN 1463-9262
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Krishna, Siddarth H., De bruyn, Mario, Schmidt, Zachary R., Weckhuysen, Bert M., Dumesic, James A., and Huber, George W. Catalytic production of hexane-1,2,5,6-tetrol from bio-renewable levoglucosanol in water: effect of metal and acid sites on (stereo)-selectivity. United States: N. p., 2018. Web. doi:10.1039/C8GC02455C.
Krishna, Siddarth H., De bruyn, Mario, Schmidt, Zachary R., Weckhuysen, Bert M., Dumesic, James A., & Huber, George W. Catalytic production of hexane-1,2,5,6-tetrol from bio-renewable levoglucosanol in water: effect of metal and acid sites on (stereo)-selectivity. United States. https://doi.org/10.1039/C8GC02455C
Krishna, Siddarth H., De bruyn, Mario, Schmidt, Zachary R., Weckhuysen, Bert M., Dumesic, James A., and Huber, George W. Tue . "Catalytic production of hexane-1,2,5,6-tetrol from bio-renewable levoglucosanol in water: effect of metal and acid sites on (stereo)-selectivity". United States. https://doi.org/10.1039/C8GC02455C. https://www.osti.gov/servlets/purl/1477860.
@article{osti_1477860,
title = {Catalytic production of hexane-1,2,5,6-tetrol from bio-renewable levoglucosanol in water: effect of metal and acid sites on (stereo)-selectivity},
author = {Krishna, Siddarth H. and De bruyn, Mario and Schmidt, Zachary R. and Weckhuysen, Bert M. and Dumesic, James A. and Huber, George W.},
abstractNote = {In this article, we report on a new route to produce hexane-1,2,5,6-tetrol (tetrol) from cellulose-derived levoglucosanol (lgol). We investigate the reaction intermediates formed over metal and acid catalysts, and propose a reaction network for this process. Lgol is converted to tetrol in up to 90% yield over a bifunctional Pt/SiO2–Al2O3 catalyst at 150 °C. High tetrol yields are maintained at lgol concentrations of up to 21 wt% in water. threo- and erythro-lgol first undergo hydrolysis to 3,4-dideoxymannose (DDM) and 3,4-dideoxyglucose (DDG), respectively. This reaction can be carried out selectively over an Amberlyst 70 acid catalyst at a temperature of 100 °C. At a higher temperature of 150 °C with no added catalyst, DDM and DDG undergo aldose–ketose isomerization to 3,4-dideoxyfructose (DDF). DDM is hydrogenated to cis-tetrol over a Pt/SiO2 catalyst, while DDG is hydrogenated to trans-tetrol. Formation of DDF erases the stereocenter at the C2 position of lgol, and hydrogenation of DDF produces a nearly 1:1 mixture of cis- and trans-tetrol. Lastly, this catalytic approach to produce tetrol from biomass opens the door to sustainable chemicals derived from tetrol.},
doi = {10.1039/C8GC02455C},
url = {https://www.osti.gov/biblio/1477860}, journal = {Green Chemistry},
issn = {1463-9262},
number = 19,
volume = 20,
place = {United States},
year = {2018},
month = {9}
}

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Cited by: 4 works
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    Works referencing / citing this record:

    Catalytic hydrogenation of dihydrolevoglucosenone to levoglucosanol with a hydrotalcite/mixed oxide copper catalyst
    journal, January 2019