title: Non-enzymatic reduction of quinone methides during oxidative coupling of monolignols: implications for the origin of benzyl structures in lignins.
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 beta-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 beta-beta-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.
authors.affiliation: Department of Fiber and Polymer Technology, School of Chemical Sciences, Royal Institute of Technology, KTH, 100 44 Stockholm, Sweden.
authors.forename: Anders
authors.initials: A
authors.lastname: Holmgren
authors.forename: Gösta
authors.initials: G
authors.lastname: Brunow
authors.forename: Gunnar
authors.initials: G
authors.lastname: Henriksson
authors.forename: Liming
authors.initials: L
authors.lastname: Zhang
authors.forename: John
authors.initials: J
authors.lastname: Ralph
mesh_terms: D001554:Benzene / Q000737:chemistry*; D002849:Chromatography, Gas; D004583:Electrons; D006140:Guaifenesin / Q000031:analogs & derivatives / Q000737:chemistry; D006865:Hydrogenation; D045563:Indolequinones / Q000737:chemistry / Q000378:metabolism*; D008031:Lignin / Q000737:chemistry* / Q000378:metabolism*; D019906:Nuclear Magnetic Resonance, Biomolecular; D010084:Oxidation-Reduction; D011108:Polymers / Q000737:chemistry
chemical_list: D045563:Indolequinones; D011108:Polymers; C068040:quinone methide; D006140:Guaifenesin; C046052:guaiacylglycerol-beta-guaiacyl ether; D008031:Lignin; D001554:Benzene