Issue 18, 2006
From the journal:

Organic & Biomolecular Chemistry

Non-enzymatic reduction of quinone methides during oxidative coupling of monolignols: implications for the origin of benzyl structures in lignins†

Anders Holmgren,a   Gösta Brunow,b   Gunnar Henriksson,a   Liming Zhang*a  and  John Ralphc  

* Corresponding authors

a Department of Fiber and Polymer Technology, School of Chemical Sciences, Royal Institute of Technology, KTH, 100 44 Stockholm, Sweden
E-mail: liming@polymer.kth.se
Fax: +46 8 7096166

b Department of Chemistry, University of Helsinki, Helsinki, Finland

c US Dairy Forage Research Center, USDA-Agricultural Research Service, Madison, USA

Abstract

Lignin is believed to be synthesized by oxidative coupling of 4-hydroxyphenylpropanoids. In native lignin there are some types of reduced structures that cannot be explained solely by oxidative coupling. In the present work we showed via biomimetic model experiments that nicotinamide adenine dinucleotide (NADH), in an uncatalyzed process, reduced a β-aryl ether quinone methide to its benzyl derivative. A number of other biologically significant reductants, including the enzyme cellobiose dehydrogenase, failed to produce the reduced structures. Synthetic dehydrogenation polymers of coniferyl alcohol synthesized (under oxidative conditions) in the presence of the reductant NADH produced the same kind of reduced structures as in the model experiment, demonstrating that oxidative and reductive processes can occur in the same environment, and that reduction of the in situ-generated quinone methides was sufficiently competitive with water addition. In situ reduction of β–β-quinone methides was not achieved in this study. The origin of racemic benzyl structures in lignins therefore remains unknown, but the potential for simple chemical reduction is demonstrated here.

Graphical abstract: Non-enzymatic reduction of quinone methides during oxidative coupling of monolignols: implications for the origin of benzyl structures in lignins

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Article information

DOI
https://doi.org/10.1039/B606369A
Article type
Paper
Submitted
05 May 2006
Accepted
30 Jun 2006
First published
07 Aug 2006

Org. Biomol. Chem., 2006,4, 3456-3461

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Non-enzymatic reduction of quinone methides during oxidative coupling of monolignols: implications for the origin of benzyl structures in lignins

A. Holmgren, G. Brunow, G. Henriksson, L. Zhang and J. Ralph, Org. Biomol. Chem., 2006, 4, 3456 DOI: 10.1039/B606369A

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