Selective Oxidation of Lignin Model Compounds

Gao, Ruili; Li, Yanding; Kim, Hoon; Mobley, Justin K.; Ralph, John

doi:10.1002/cssc.201800598

Title: Selective Oxidation of Lignin Model Compounds

Journal Article · Wed May 30 00:00:00 EDT 2018 · ChemSusChem

DOI:https://doi.org/10.1002/cssc.201800598· OSTI ID:1459426

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Univ. of Wisconsin, Madison, WI (United States). Dept. of Biochemistry
Univ. of Wisconsin, Madison, WI (United States). Wisconsin Energy Inst., DOE Great Lakes Bioenergy Research Center, and Dept. of Biological Systems Engineering
Univ. of Wisconsin, Madison, WI (United States). Wisconsin Energy Inst., DOE Great Lakes Bioenergy Research Center

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 ₂ Cl 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. 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.

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Research Organization:: Univ. of Wisconsin, Madison, WI (United States). Great Lakes Bioenergy Research Center

Sponsoring Organization:: USDOE Office of Science (SC), Biological and Environmental Research (BER)

Grant/Contract Number:: SC0018409; FC02-07ER64494

OSTI ID:: 1459426

Alternate ID(s):: OSTI ID: 1493465

Journal Information:: ChemSusChem, Vol. 11, Issue 13; ISSN 1864-5631

Publisher:: ChemPubSoc EuropeCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 31 works

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References (48)

Lignin Valorization: Improving Lignin Processing in the Biorefinery Ragauskas, A. J.; Beckham, G. T.; Biddy, M. J. Science, Vol. 344, Issue 6185, p. 1246843-1246843 https://doi.org/10.1126/science.1246843	journal	May 2014
Lignin Biosynthesis Boerjan, Wout; Ralph, John; Baucher, Marie Annual Review of Plant Biology, Vol. 54, Issue 1, p. 519-546 https://doi.org/10.1146/annurev.arplant.54.031902.134938	journal	June 2003
Aerobic oxidation of benzyl alcohols by MoVI compounds Jeyakumar, Kandasamy; Chand, Dillip Kumar Applied Organometallic Chemistry, Vol. 20, Issue 12 https://doi.org/10.1002/aoc.1141	journal	January 2006
Knocking on Wood: Base Metal Complexes as Catalysts for Selective Oxidation of Lignin Models and Extracts Hanson, Susan K.; Baker, R. Tom Accounts of Chemical Research, Vol. 48, Issue 7 https://doi.org/10.1021/acs.accounts.5b00104	journal	June 2015
C-C or C-O Bond Cleavage in a Phenolic Lignin Model Compound: Selectivity Depends on Vanadium Catalyst Hanson, Susan K.; Wu, Ruilian; Silks, Louis A. “Pete” Angewandte Chemie International Edition, Vol. 51, Issue 14, p. 3410-3413 https://doi.org/10.1002/anie.201107020	journal	January 2012
Copper- and Vanadium-Catalyzed Oxidative Cleavage of Lignin using Dioxygen Mottweiler, Jakob; Puche, Marta; Räuber, Christoph ChemSusChem, Vol. 8, Issue 12 https://doi.org/10.1002/cssc.201500131	journal	May 2015
Modified lignin in tobacco and poplar plants over-expressing the Arabidopsis gene encoding ferulate 5-hydroxylase Franke, Rochus; McMichael, Colleen M.; Meyer, Knut The Plant Journal, Vol. 22, Issue 3, p. 223-234 https://doi.org/10.1046/j.1365-313x.2000.00727.x	journal	May 2000
Alkaline Hydrolysis of Nonphenolic α-Carbonyl β-0-4 Lignin Dimers Substituted on the Leaving Phenoxide Ring: Comparison with Benzylic Hydroxyl Analogues Criss, Dexter L.; Fisher, Thomas H.; Schultz, Tor P. Holzforschung, Vol. 52, Issue 1 https://doi.org/10.1515/hfsg.1998.52.1.57	journal	January 1998
Simple and Selective Oxidation of Thiols to Disulfides with Dimethylsulfoxide Catalyzed by Dichlorodioxomolybdenum(VI) Sanz, Roberto; Aguado, Rafael; Pedrosa, María R. Synthesis, Vol. 2002, Issue 07 https://doi.org/10.1055/s-2002-28520	journal	January 2002
Formic-acid-induced depolymerization of oxidized lignin to aromatics Rahimi, Alireza; Ulbrich, Arne; Coon, Joshua J. Nature, Vol. 515, Issue 7526, p. 249-252 https://doi.org/10.1038/nature13867	journal	November 2014
Comparison of Copper and Vanadium Homogeneous Catalysts for Aerobic Oxidation of Lignin Models Sedai, Baburam; Díaz-Urrutia, Christian; Baker, R. Tom ACS Catalysis, Vol. 1, Issue 7 https://doi.org/10.1021/cs200149v	journal	May 2011
Bright Side of Lignin Depolymerization: Toward New Platform Chemicals Sun, Zhuohua; Fridrich, Bálint; de Santi, Alessandra Chemical Reviews, Vol. 118, Issue 2 https://doi.org/10.1021/acs.chemrev.7b00588	journal	January 2018
Isolation of Functionalized Phenolic Monomers through Selective Oxidation and CO Bond Cleavage of the β-O-4 Linkages in Lignin Lancefield, Christopher S.; Ojo, O. Stephen; Tran, Fanny Angewandte Chemie International Edition, Vol. 54, Issue 1 https://doi.org/10.1002/anie.201409408	journal	November 2014
Isolation of Functionalized Phenolic Monomers through Selective Oxidation and CO Bond Cleavage of the β-O-4 Linkages in Lignin Lancefield, Christopher S.; Ojo, O. Stephen; Tran, Fanny Angewandte Chemie, Vol. 127, Issue 1 https://doi.org/10.1002/ange.201409408	journal	November 2014
Wege zur Verwertung von Lignin: Fortschritte in der Biotechnik, der Bioraffination und der Katalyse Rinaldi, Roberto; Jastrzebski, Robin; Clough, Matthew T. Angewandte Chemie, Vol. 128, Issue 29 https://doi.org/10.1002/ange.201510351	journal	June 2016
Microwave assisted oxidation of a lignin model phenolic monomer using Co(salen)/SBA-15 Badamali, S.; Luque, R.; Clark, J. Catalysis Communications, Vol. 10, Issue 6 https://doi.org/10.1016/j.catcom.2008.12.051	journal	February 2009
Application of molybdenum(VI) dichloride dioxide (MoO2Cl2) in organic transformations Jeyakumar, Kandasamy; Chand, Dillip K. Journal of Chemical Sciences, Vol. 121, Issue 2 https://doi.org/10.1007/s12039-009-0013-z	journal	March 2009
Hierarchical Self-Assembly of Donor–Acceptor-Substituted Butadiene Amphiphiles into Photoresponsive Vesicles and Gels Kumar, N. S. Saleesh; Varghese, Shinto; Narayan, Gopinathan Angewandte Chemie, Vol. 118, Issue 38 https://doi.org/10.1002/ange.200602088	journal	September 2006
The Catalytic Valorization of Lignin for the Production of Renewable Chemicals Zakzeski, Joseph; Bruijnincx, Pieter C. A.; Jongerius, Anna L. Chemical Reviews, Vol. 110, Issue 6, p. 3552-3599 https://doi.org/10.1021/cr900354u	journal	June 2010
Highly effective C–C bond cleavage of lignin model compounds Wang, Yinling; Wang, Qianyi; He, Jianghua Green Chemistry, Vol. 19, Issue 13 https://doi.org/10.1039/C7GC00844A	journal	January 2017
Catalytic Transformation of Lignin for the Production of Chemicals and Fuels Li, Changzhi; Zhao, Xiaochen; Wang, Aiqin Chemical Reviews, Vol. 115, Issue 21, p. 11559-11624 https://doi.org/10.1021/acs.chemrev.5b00155	journal	October 2015
Catalytic Lignin Valorization Process for the Production of Aromatic Chemicals and Hydrogen Zakzeski, Joseph; Jongerius, Anna L.; Bruijnincx, Pieter C. A. ChemSusChem, Vol. 5, Issue 8 https://doi.org/10.1002/cssc.201100699	journal	June 2012
Iron( iii ) and cobalt( iii ) complexes with both tautomeric (keto and enol) forms of aroylhydrazone ligands: catalysts for the microwave assisted oxidation of alcohols Sutradhar, Manas; Alegria, Elisabete C. B. A.; Mahmudov, Kamran T. RSC Advances, Vol. 6, Issue 10 https://doi.org/10.1039/C5RA25774C	journal	January 2016
The Effects on Lignin Structure of Overexpression of Ferulate 5-Hydroxylase in Hybrid Poplar ¹ Stewart, Jaclyn J.; Akiyama, Takuya; Chapple, Clint Plant Physiology, Vol. 150, Issue 2 https://doi.org/10.1104/pp.109.137059	journal	April 2009
The Path Forward for Biofuels and Biomaterials Ragauskas, Arthur J.; Williams, Charlotte K.; Davison, Brian H. Science, Vol. 311, Issue 5760, p. 484-489 https://doi.org/10.1126/science.1114736	journal	January 2006
Hierarchical Self-Assembly of Donor–Acceptor-Substituted Butadiene Amphiphiles into Photoresponsive Vesicles and Gels Kumar, N. S. Saleesh; Varghese, Shinto; Narayan, Gopinathan Angewandte Chemie International Edition, Vol. 45, Issue 38 https://doi.org/10.1002/anie.200602088	journal	September 2006
Adducts of anthrahydroquinone and anthranol with lignin model quinone methides. 3. Independent synthesis of threo and erythro isomers Ralph, John; Landucci, Lawrence L. The Journal of Organic Chemistry, Vol. 48, Issue 22 https://doi.org/10.1021/jo00170a003	journal	November 1983
Selective Deoxygenation of Sulfoxides to Sulfides with Phosphites Catalyzed by Dichlorodioxomolybdenum(VI) Sanz, Roberto; Escribano, Jaime; Aguado, Rafael Synthesis, Vol. 2004, Issue 10 https://doi.org/10.1055/s-2004-829104	journal	June 2004
Determination of the Conformation and Isomeric Composition of Lignin Model Quinone Methides By NMR Ralph, John; Adams, Bruce R. Journal of Wood Chemistry and Technology, Vol. 3, Issue 2 https://doi.org/10.1080/02773818308085159	journal	January 1983
Paving the Way for Lignin Valorisation: Recent Advances in Bioengineering, Biorefining and Catalysis Rinaldi, Roberto; Jastrzebski, Robin; Clough, Matthew T. Angewandte Chemie International Edition, Vol. 55, Issue 29 https://doi.org/10.1002/anie.201510351	journal	June 2016
Nucleophilic Acyl Substitutions of Esters with Protic Nucleophiles Mediated by Amphoteric, Oxotitanium, and Vanadyl Species Chen, Chien-Tien; Kuo, Jen-Huang; Ku, Cheng-Hsiu The Journal of Organic Chemistry, Vol. 70, Issue 4 https://doi.org/10.1021/jo0484878	journal	February 2005
Stereochemical Aspects Op Addition Reactions Involving Lignin Model Quinone Methides Ralph, John; Young, Raymond A. Journal of Wood Chemistry and Technology, Vol. 3, Issue 2 https://doi.org/10.1080/02773818308085158	journal	January 1983
Chemoselective Metal-Free Aerobic Alcohol Oxidation in Lignin Rahimi, Alireza; Azarpira, Ali; Kim, Hoon Journal of the American Chemical Society, Vol. 135, Issue 17, p. 6415-6418 https://doi.org/10.1021/ja401793n	journal	April 2013
Efficient Cobalt-Catalyzed Oxidative Conversion of Lignin Models to Benzoquinones Biannic, Berenger; Bozell, Joseph J. Organic Letters, Vol. 15, Issue 11 https://doi.org/10.1021/ol401065r	journal	May 2013
Synthetic Analogues and Reaction Systems Relevant to the Molybdenum and Tungsten Oxotransferases Enemark, John H.; Cooney, J. Jon A.; Wang, Jun-Jieh Chemical Reviews, Vol. 104, Issue 2 https://doi.org/10.1021/cr020609d	journal	February 2004
Aerobic Oxidation of β-1 Lignin Model Compounds with Copper and Oxovanadium Catalysts Sedai, Baburam; Díaz-Urrutia, Christian; Baker, R. Tom ACS Catalysis, Vol. 3, Issue 12 https://doi.org/10.1021/cs400636k	journal	November 2013
Cooperative electrocatalytic alcohol oxidation with electron-proton-transfer mediators Badalyan, Artavazd; Stahl, Shannon S. Nature, Vol. 535, Issue 7612 https://doi.org/10.1038/nature18008	journal	June 2016
Significant Lability of Guaiacylglycerol β-Phenacyl Ether under Alkaline Conditions Imai, Aiko; Yokoyama, Tomoya; Matsumoto, Yuji Journal of Agricultural and Food Chemistry, Vol. 55, Issue 22 https://doi.org/10.1021/jf071147d	journal	October 2007
Formaldehyde stabilization facilitates lignin monomer production during biomass depolymerization Shuai, Li; Amiri, Masoud Talebi; Questell-Santiago, Ydna M. Science, Vol. 354, Issue 6310 https://doi.org/10.1126/science.aaf7810	journal	October 2016
Two-Step, Catalytic C–C Bond Oxidative Cleavage Process Converts Lignin Models and Extracts to Aromatic Acids Wang, Min; Lu, Jianmin; Zhang, Xiaochen ACS Catalysis, Vol. 6, Issue 9 https://doi.org/10.1021/acscatal.6b02049	journal	August 2016
Oxidation of lignin and lignin β-O-4 model compounds via activated dimethyl sulfoxide Mobley, Justin K.; Yao, Soledad G.; Crocker, Mark RSC Advances, Vol. 5, Issue 127 https://doi.org/10.1039/C5RA33240K	journal	January 2015
CC or CO Bond Cleavage in a Phenolic Lignin Model Compound: Selectivity Depends on Vanadium Catalyst Hanson, Susan K.; Wu, Ruilian; Silks, Louis A. “Pete” Angewandte Chemie, Vol. 124, Issue 14 https://doi.org/10.1002/ange.201107020	journal	January 2012
Catalytic Oxidation of Biorefinery Lignin to Value-added Chemicals to Support Sustainable Biofuel Production Ma, Ruoshui; Xu, Yan; Zhang, Xiao ChemSusChem, Vol. 8, Issue 1 https://doi.org/10.1002/cssc.201402503	journal	October 2014
A selective, efficient and environmentally friendly method for the oxidative cleavage of glycols García, Nuria; Rubio-Presa, Rubén; García-García, Patricia Green Chemistry, Vol. 18, Issue 8 https://doi.org/10.1039/C5GC02862K	journal	January 2016
A microwave approach to the selective synthesis of ω-laurolactam Conesa, Tomas D.; Campelo, Juan M.; Clark, James H. Green Chemistry, Vol. 9, Issue 10 https://doi.org/10.1039/b705881k	journal	January 2007
Synthetic Analogues and Reaction Systems Relevant to the Molybdenum and Tungsten Oxotransferases Enemark, John H.; Cooney, J. Jon A.; Wang, Jun-Jieh ChemInform, Vol. 35, Issue 21 https://doi.org/10.1002/chin.200421281	journal	May 2004
Nucleophilic Acyl Substitutions of Esters with Protic Nucleophiles Mediated by Amphoteric, Oxotitanium, and Vanadyl Species. Chen, Chien-Tien; Kuo, Jen-Huang; Ku, Cheng-Hsiu ChemInform, Vol. 36, Issue 28 https://doi.org/10.1002/chin.200528032	journal	July 2005
Selective Deoxygenation of Sulfoxides to Sulfides with Phosphites Catalyzed by Dichlorodioxomolybdenum(VI). Sanz, Roberto; Escribano, Jaime; Aguado, Rafael ChemInform, Vol. 35, Issue 45 https://doi.org/10.1002/chin.200445098	journal	November 2004

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