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Title: Selective Oxidation of Lignin Model Compounds

Abstract

Lignin, the planet's most abundant renewable source of aromatic compounds, is difficult to degrade efficiently to welldefined aromatics. We developed a microwave-assisted catalytic Swern oxidation system using an easily prepared catalyst, MoO 2Cl 2(DMSO) 2, and DMSO as the solvent and oxidant. It demonstrated high efficiency in transforming lignin model compounds containing the units and functional groups found in native lignins. The aromatic ring substituents strongly influenced the selectivity of β-ether phenolic dimer cleavage to generate sinapaldehyde and coniferaldehyde, monomers not usually produced by oxidative methods. Time-course studies on two key intermediates provided insight into the reaction pathway. Finally, owing to the broad scope of this oxidation system and the insight gleaned with regard to its mechanism, this strategy could be adapted and applied in a general sense to the production of useful aromatic chemicals from phenolics and lignin.

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [1]; ORCiD logo [3]; ORCiD logo [1]
  1. Univ. of Wisconsin, Madison, WI (United States). Dept. of Biochemistry
  2. Univ. of Wisconsin, Madison, WI (United States). Wisconsin Energy Inst., DOE Great Lakes Bioenergy Research Center, and Dept. of Biological Systems Engineering
  3. Univ. of Wisconsin, Madison, WI (United States). Wisconsin Energy Inst., DOE Great Lakes Bioenergy Research Center
Publication Date:
Research Org.:
Univ. of Wisconsin, Madison, WI (United States). Great Lakes Bioenergy Research Center
Sponsoring Org.:
USDOE Office of Science (SC), Biological and Environmental Research (BER) (SC-23)
OSTI Identifier:
1459426
Alternate Identifier(s):
OSTI ID: 1493465
Grant/Contract Number:  
SC0018409; FC02-07ER64494
Resource Type:
Accepted Manuscript
Journal Name:
ChemSusChem
Additional Journal Information:
Journal Volume: 11; Journal Issue: 13; Journal ID: ISSN 1864-5631
Publisher:
ChemPubSoc Europe
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Swern oxidation; microwave irradiation; sinapaldehyde; coniferaldehyde; lignin monomer

Citation Formats

Gao, Ruili, Li, Yanding, Kim, Hoon, Mobley, Justin K., and Ralph, John. Selective Oxidation of Lignin Model Compounds. United States: N. p., 2018. Web. doi:10.1002/cssc.201800598.
Gao, Ruili, Li, Yanding, Kim, Hoon, Mobley, Justin K., & Ralph, John. Selective Oxidation of Lignin Model Compounds. United States. doi:10.1002/cssc.201800598.
Gao, Ruili, Li, Yanding, Kim, Hoon, Mobley, Justin K., and Ralph, John. Wed . "Selective Oxidation of Lignin Model Compounds". United States. doi:10.1002/cssc.201800598. https://www.osti.gov/servlets/purl/1459426.
@article{osti_1459426,
title = {Selective Oxidation of Lignin Model Compounds},
author = {Gao, Ruili and Li, Yanding and Kim, Hoon and Mobley, Justin K. and Ralph, John},
abstractNote = {Lignin, the planet's most abundant renewable source of aromatic compounds, is difficult to degrade efficiently to welldefined aromatics. We developed a microwave-assisted catalytic Swern oxidation system using an easily prepared catalyst, MoO2Cl2(DMSO)2, and DMSO as the solvent and oxidant. It demonstrated high efficiency in transforming lignin model compounds containing the units and functional groups found in native lignins. The aromatic ring substituents strongly influenced the selectivity of β-ether phenolic dimer cleavage to generate sinapaldehyde and coniferaldehyde, monomers not usually produced by oxidative methods. Time-course studies on two key intermediates provided insight into the reaction pathway. Finally, owing to the broad scope of this oxidation system and the insight gleaned with regard to its mechanism, this strategy could be adapted and applied in a general sense to the production of useful aromatic chemicals from phenolics and lignin.},
doi = {10.1002/cssc.201800598},
journal = {ChemSusChem},
number = 13,
volume = 11,
place = {United States},
year = {2018},
month = {5}
}

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Cited by: 5 works
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    Works referencing / citing this record:

    Kinetic and mechanistic insights into hydrogenolysis of lignin to monomers in a continuous flow reactor
    journal, January 2019

    • Li, Yanding; Demir, Benginur; Vázquez Ramos, Leida M.
    • Green Chemistry, Vol. 21, Issue 13
    • DOI: 10.1039/c9gc00986h

    Heterogeneous Catalyzed Thermochemical Conversion of Lignin Model Compounds: An Overview
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