Radical Coupling Reactions of Hydroxystilbene Glucosides and Coniferyl Alcohol: A Density Functional Theory Study
The monolignols, p-coumaryl, coniferyl, and sinapyl alcohol, arise from the general phenylpropanoid biosynthetic pathway. Increasingly, however, authentic lignin monomers derived from outside this process are being identified and found to be fully incorporated into the lignin polymer. Among them, hy...
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doaj-f1ee611f9c4f47e5babbc532ab8198202021-03-02T07:32:40ZengFrontiers Media S.A.Frontiers in Plant Science1664-462X2021-03-011210.3389/fpls.2021.642848642848Radical Coupling Reactions of Hydroxystilbene Glucosides and Coniferyl Alcohol: A Density Functional Theory StudyThomas Elder0Jorge Rencoret1José C. del Río2Hoon Kim3John Ralph4John Ralph5USDA-Forest Service, Southern Research Station, Auburn, AL, United StatesInstituto de Recursos Naturales y Agrobiología de Sevilla, CSIC, Seville, SpainInstituto de Recursos Naturales y Agrobiología de Sevilla, CSIC, Seville, SpainDepartment of Energy Great Lakes Bioenergy Research Center, Wisconsin Energy Institute, University of Wisconsin, Madison, WI, United StatesDepartment of Energy Great Lakes Bioenergy Research Center, Wisconsin Energy Institute, University of Wisconsin, Madison, WI, United StatesDepartment of Biochemistry, University of Wisconsin, Madison, WI, United StatesThe monolignols, p-coumaryl, coniferyl, and sinapyl alcohol, arise from the general phenylpropanoid biosynthetic pathway. Increasingly, however, authentic lignin monomers derived from outside this process are being identified and found to be fully incorporated into the lignin polymer. Among them, hydroxystilbene glucosides, which are produced through a hybrid process that combines the phenylpropanoid and acetate/malonate pathways, have been experimentally detected in the bark lignin of Norway spruce (Picea abies). Several interunit linkages have been identified and proposed to occur through homo-coupling of the hydroxystilbene glucosides and their cross-coupling with coniferyl alcohol. In the current work, the thermodynamics of these coupling modes and subsequent rearomatization reactions have been evaluated by the application of density functional theory (DFT) calculations. The objective of this paper is to determine favorable coupling and cross-coupling modes to help explain the experimental observations and attempt to predict other favorable pathways that might be further elucidated via in vitro polymerization aided by synthetic models and detailed structural studies.https://www.frontiersin.org/articles/10.3389/fpls.2021.642848/fullligninhydroxystilbene glucosidesdensity functional theoryquinone methidesrearomatization |
collection |
DOAJ |
language |
English |
format |
Article |
sources |
DOAJ |
author |
Thomas Elder Jorge Rencoret José C. del Río Hoon Kim John Ralph John Ralph |
spellingShingle |
Thomas Elder Jorge Rencoret José C. del Río Hoon Kim John Ralph John Ralph Radical Coupling Reactions of Hydroxystilbene Glucosides and Coniferyl Alcohol: A Density Functional Theory Study Frontiers in Plant Science lignin hydroxystilbene glucosides density functional theory quinone methides rearomatization |
author_facet |
Thomas Elder Jorge Rencoret José C. del Río Hoon Kim John Ralph John Ralph |
author_sort |
Thomas Elder |
title |
Radical Coupling Reactions of Hydroxystilbene Glucosides and Coniferyl Alcohol: A Density Functional Theory Study |
title_short |
Radical Coupling Reactions of Hydroxystilbene Glucosides and Coniferyl Alcohol: A Density Functional Theory Study |
title_full |
Radical Coupling Reactions of Hydroxystilbene Glucosides and Coniferyl Alcohol: A Density Functional Theory Study |
title_fullStr |
Radical Coupling Reactions of Hydroxystilbene Glucosides and Coniferyl Alcohol: A Density Functional Theory Study |
title_full_unstemmed |
Radical Coupling Reactions of Hydroxystilbene Glucosides and Coniferyl Alcohol: A Density Functional Theory Study |
title_sort |
radical coupling reactions of hydroxystilbene glucosides and coniferyl alcohol: a density functional theory study |
publisher |
Frontiers Media S.A. |
series |
Frontiers in Plant Science |
issn |
1664-462X |
publishDate |
2021-03-01 |
description |
The monolignols, p-coumaryl, coniferyl, and sinapyl alcohol, arise from the general phenylpropanoid biosynthetic pathway. Increasingly, however, authentic lignin monomers derived from outside this process are being identified and found to be fully incorporated into the lignin polymer. Among them, hydroxystilbene glucosides, which are produced through a hybrid process that combines the phenylpropanoid and acetate/malonate pathways, have been experimentally detected in the bark lignin of Norway spruce (Picea abies). Several interunit linkages have been identified and proposed to occur through homo-coupling of the hydroxystilbene glucosides and their cross-coupling with coniferyl alcohol. In the current work, the thermodynamics of these coupling modes and subsequent rearomatization reactions have been evaluated by the application of density functional theory (DFT) calculations. The objective of this paper is to determine favorable coupling and cross-coupling modes to help explain the experimental observations and attempt to predict other favorable pathways that might be further elucidated via in vitro polymerization aided by synthetic models and detailed structural studies. |
topic |
lignin hydroxystilbene glucosides density functional theory quinone methides rearomatization |
url |
https://www.frontiersin.org/articles/10.3389/fpls.2021.642848/full |
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