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Title: Coupling and Reactions of 5-Hydroxyconiferyl Alcohol in Lignin Formation

Abstract

The catechol alcohols, caffeyl and 5-hydroxyconiferyl alcohol, may be incorporated into lignin either naturally or through genetic manipulation. Due to the presence of o-OH groups, these compounds form benzodioxanes, a departure from the interunit connections found in lignins derived from the cinnamyl alcohols. In nature, lignins composed of caffeyl and 5-hydroxyconiferyl alcohol are linear homopolymers and, as such, may have properties that make them amenable for use in value-added products, such as lignin-based carbon fibers. In the current work, results from density functional theory calculations for the reactions of 5-hydroxyconiferyl alcohol, taking stereochemistry into account, are reported. Dehydrogenation and quinone methide formation are found to be thermodynamically favored for 5-hydroxyconiferyl alcohol, over coniferyl alcohol. The comparative energetics of the rearomatization reactions suggest that the formation of the benzodioxane linkage is under kinetic control. Ring-opening reactions of the benzodioxane groups show that the bond dissociation enthalpy of the $$\alpha$$-O cleavage reaction is lower than that of the $$\beta$$-O reaction. In conclusion, the catechol lignins represent a novel form of the polymer that may offer new opportunities for bioproducts and genetic targets.

Authors:
 [1];  [2];  [2];  [3]
  1. USDA-Forest Service, Auburn, AL (United States). Southern Research Station
  2. National Renewable Energy Lab. (NREL), Golden, CO (United States). National Bioenergy Center
  3. National Renewable Energy Lab. (NREL), Golden, CO (United States). Biosciences Center
Publication Date:
Research Org.:
National Renewable Energy Lab. (NREL), Golden, CO (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE)
OSTI Identifier:
1259259
Report Number(s):
NREL/JA-5100-66685
Journal ID: ISSN 0021-8561
Grant/Contract Number:  
AC36-08GO28308
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Agricultural and Food Chemistry
Additional Journal Information:
Journal Volume: 64; Journal Issue: 23; Journal ID: ISSN 0021-8561
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 5-hydroxyconiferyl alcohol; benzodioxane; coniferyl alcohol; lignin; stereochemistry

Citation Formats

Elder, Thomas, Berstis, Laura, Beckham, Gregg T., and Crowley, Michael F. Coupling and Reactions of 5-Hydroxyconiferyl Alcohol in Lignin Formation. United States: N. p., 2016. Web. https://doi.org/10.1021/acs.jafc.6b02234.
Elder, Thomas, Berstis, Laura, Beckham, Gregg T., & Crowley, Michael F. Coupling and Reactions of 5-Hydroxyconiferyl Alcohol in Lignin Formation. United States. https://doi.org/10.1021/acs.jafc.6b02234
Elder, Thomas, Berstis, Laura, Beckham, Gregg T., and Crowley, Michael F. Sat . "Coupling and Reactions of 5-Hydroxyconiferyl Alcohol in Lignin Formation". United States. https://doi.org/10.1021/acs.jafc.6b02234. https://www.osti.gov/servlets/purl/1259259.
@article{osti_1259259,
title = {Coupling and Reactions of 5-Hydroxyconiferyl Alcohol in Lignin Formation},
author = {Elder, Thomas and Berstis, Laura and Beckham, Gregg T. and Crowley, Michael F.},
abstractNote = {The catechol alcohols, caffeyl and 5-hydroxyconiferyl alcohol, may be incorporated into lignin either naturally or through genetic manipulation. Due to the presence of o-OH groups, these compounds form benzodioxanes, a departure from the interunit connections found in lignins derived from the cinnamyl alcohols. In nature, lignins composed of caffeyl and 5-hydroxyconiferyl alcohol are linear homopolymers and, as such, may have properties that make them amenable for use in value-added products, such as lignin-based carbon fibers. In the current work, results from density functional theory calculations for the reactions of 5-hydroxyconiferyl alcohol, taking stereochemistry into account, are reported. Dehydrogenation and quinone methide formation are found to be thermodynamically favored for 5-hydroxyconiferyl alcohol, over coniferyl alcohol. The comparative energetics of the rearomatization reactions suggest that the formation of the benzodioxane linkage is under kinetic control. Ring-opening reactions of the benzodioxane groups show that the bond dissociation enthalpy of the $\alpha$-O cleavage reaction is lower than that of the $\beta$-O reaction. In conclusion, the catechol lignins represent a novel form of the polymer that may offer new opportunities for bioproducts and genetic targets.},
doi = {10.1021/acs.jafc.6b02234},
journal = {Journal of Agricultural and Food Chemistry},
number = 23,
volume = 64,
place = {United States},
year = {2016},
month = {5}
}

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Works referenced in this record:

Lignin Biosynthesis
journal, June 2003


Metabolic engineering of novel lignin in biomass crops
journal, October 2012


Superior plant based carbon fibers from electrospun poly-(caffeyl alcohol) lignin
journal, July 2016


A polymer of caffeyl alcohol in plant seeds
journal, January 2012

  • Chen, F.; Tobimatsu, Y.; Havkin-Frenkel, D.
  • Proceedings of the National Academy of Sciences, Vol. 109, Issue 5
  • DOI: 10.1073/pnas.1120992109

Phenolic Profiling of Caffeic Acid O -Methyltransferase-Deficient Poplar Reveals Novel Benzodioxane Oligolignols
journal, November 2004

  • Morreel, Kris; Ralph, John; Lu, Fachuang
  • Plant Physiology, Vol. 136, Issue 4
  • DOI: 10.1104/pp.104.049312

Sequencing around 5-Hydroxyconiferyl Alcohol-Derived Units in Caffeic Acid O -Methyltransferase-Deficient Poplar Lignins
journal, April 2010

  • Lu, Fachuang; Marita, Jane M.; Lapierre, Catherine
  • Plant Physiology, Vol. 153, Issue 2
  • DOI: 10.1104/pp.110.154278

CCoAOMT suppression modifies lignin composition in Pinus radiata
journal, April 2011


Novel seed coat lignins in the Cactaceae: structure, distribution and implications for the evolution of lignin diversity
journal, November 2012

  • Chen, Fang; Tobimatsu, Yuki; Jackson, Lisa
  • The Plant Journal, Vol. 73, Issue 2
  • DOI: 10.1111/tpj.12012

Radical Coupling Reactions in Lignin Synthesis: A Density Functional Theory Study
journal, April 2012

  • Sangha, Amandeep K.; Parks, Jerry M.; Standaert, Robert F.
  • The Journal of Physical Chemistry B, Vol. 116, Issue 16
  • DOI: 10.1021/jp2122449

Chemical Factors that Control Lignin Polymerization
journal, December 2013

  • Sangha, Amandeep K.; Davison, Brian H.; Standaert, Robert F.
  • The Journal of Physical Chemistry B, Vol. 118, Issue 1
  • DOI: 10.1021/jp411998t

Theoretical Study of the Remarkably Diverse Linkages in Lignin
journal, October 2011

  • Parthasarathi, R.; Romero, Raymond A.; Redondo, Antonio
  • The Journal of Physical Chemistry Letters, Vol. 2, Issue 20
  • DOI: 10.1021/jz201201q

Computational Study of Bond Dissociation Enthalpies for a Large Range of Native and Modified Lignins
journal, October 2011

  • Kim, Seonah; Chmely, Stephen C.; Nimlos, Mark R.
  • The Journal of Physical Chemistry Letters, Vol. 2, Issue 22
  • DOI: 10.1021/jz201182w

Density Functional Theory Study of the Concerted Pyrolysis Mechanism for Lignin Models
journal, July 2014

  • Elder, Thomas; Beste, Ariana
  • Energy & Fuels, Vol. 28, Issue 8
  • DOI: 10.1021/ef5013648

Kinetic Analysis of the Phenyl-Shift Reaction in β-O-4 Lignin Model Compounds: A Computational Study
journal, April 2011

  • Beste, Ariana; Buchanan, A. C.
  • The Journal of Organic Chemistry, Vol. 76, Issue 7
  • DOI: 10.1021/jo2000385

Substituent Effects on the Reaction Rates of Hydrogen Abstraction in the Pyrolysis of Phenethyl Phenyl Ethers
journal, May 2010

  • Beste, Ariana; Buchanan, A. C.
  • Energy & Fuels, Vol. 24, Issue 5
  • DOI: 10.1021/ef1001953

Computational Study of Bond Dissociation Enthalpies for Lignin Model Compounds. Substituent Effects in Phenethyl Phenyl Ethers
journal, April 2009

  • Beste, Ariana; Buchanan, A. C.
  • The Journal of Organic Chemistry, Vol. 74, Issue 7
  • DOI: 10.1021/jo9001307

Computational study of bond dissociation enthalpies for lignin model compounds: β-5 Arylcoumaran
journal, August 2012


Computational Study of Bond Dissociation Enthalpies for Substituted β-O-4 Lignin Model Compounds
journal, November 2011

  • Younker, Jarod M.; Beste, Ariana; Buchanan, A. C.
  • ChemPhysChem, Vol. 12, Issue 18
  • DOI: 10.1002/cphc.201100477

Computational Prediction of α/β Selectivities in the Pyrolysis of Oxygen-Substituted Phenethyl Phenyl Ethers
journal, June 2008

  • Beste, Ariana; Buchanan, A. C.; Harrison, Robert J.
  • The Journal of Physical Chemistry A, Vol. 112, Issue 22
  • DOI: 10.1021/jp800767j

Bond Dissociation Enthalpies of a Pinoresinol Lignin Model Compound
journal, January 2014


Bond Dissociation Enthalpies of a Dibenzodioxocin Lignin Model Compound
journal, July 2013


A computational study of pyrolysis reactions of lignin model compounds
journal, June 2010


Pyrolysis reaction networks for lignin model compounds: unraveling thermal deconstruction of β-O-4 and α-O-4 compounds
journal, January 2016

  • Choi, Yong S.; Singh, Rahul; Zhang, Jing
  • Green Chemistry, Vol. 18, Issue 6
  • DOI: 10.1039/C5GC02268A

Acidolysis of α-O-4 Aryl-Ether Bonds in Lignin Model Compounds: A Modeling and Experimental Study
journal, June 2015

  • Pelzer, Adam W.; Sturgeon, Matthew R.; Yanez, Abraham J.
  • ACS Sustainable Chemistry & Engineering, Vol. 3, Issue 7
  • DOI: 10.1021/acssuschemeng.5b00070

A Mechanistic Investigation of Acid-Catalyzed Cleavage of Aryl-Ether Linkages: Implications for Lignin Depolymerization in Acidic Environments
journal, November 2013

  • Sturgeon, Matthew R.; Kim, Seonah; Lawrence, Kelsey
  • ACS Sustainable Chemistry & Engineering, Vol. 2, Issue 3, p. 472-485
  • DOI: 10.1021/sc400384w

Lignin Formation in Plants. The Dilemma of Linkage Specificity
journal, August 2001


Exploring the Limit of Accuracy of the Global Hybrid Meta Density Functional for Main-Group Thermochemistry, Kinetics, and Noncovalent Interactions
journal, October 2008

  • Zhao, Yan; Truhlar, Donald G.
  • Journal of Chemical Theory and Computation, Vol. 4, Issue 11
  • DOI: 10.1021/ct800246v

On the distribution of the diastereomers of the structural elements in lignins: the steric course of reactions mimicking lignin biosynthesis
journal, May 1993

  • Brunow, G.; Karlsson, O.; Lundquist, K.
  • Wood Science and Technology, Vol. 27, Issue 4
  • DOI: 10.1007/BF00195305

Enzymatic dehydrogenative polymerization of monolignol dimers
journal, September 2015


Recent advances in low-cost carbon fiber manufacture from lignin
journal, April 2013

  • Baker, Darren A.; Rials, Timothy G.
  • Journal of Applied Polymer Science, Vol. 130, Issue 2
  • DOI: 10.1002/app.39273

Flash Vacuum Pyrolysis of Methoxy-Substituted Lignin Model Compounds
journal, March 2000

  • Britt, Phillip F.; Buchanan, A. C.; Cooney, Mark J.
  • The Journal of Organic Chemistry, Vol. 65, Issue 5
  • DOI: 10.1021/jo991479k

Understanding Substituent Effects in Noncovalent Interactions Involving Aromatic Rings
journal, June 2012

  • Wheeler, Steven E.
  • Accounts of Chemical Research, Vol. 46, Issue 4
  • DOI: 10.1021/ar300109n

    Works referencing / citing this record:

    Phenolic cross-links: building and de-constructing the plant cell wall
    journal, January 2020

    • Mnich, Ewelina; Bjarnholt, Nanna; Eudes, Aymerick
    • Natural Product Reports
    • DOI: 10.1039/c9np00028c