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/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.
- Authors:
-
[1];
[3];
[1]
- Univ. of Wisconsin, Madison, WI (United States). Department of Chemical and Biological Engineering
- 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
- 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), Sustainable Transportation Office. Bioenergy Technologies Office (BETO)
- 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:
- 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},
journal = {Green Chemistry},
number = 19,
volume = 20,
place = {United States},
year = {Tue Sep 11 00:00:00 EDT 2018},
month = {Tue Sep 11 00:00:00 EDT 2018}
}
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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
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