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Direct conversion of lignin to functionalized diaryl ethers via oxidative cross-coupling

Efficient valorization of lignin, a sustainable source of functionalized aromatic products, would reduce dependence on fossil-derived feedstocks. Oxidative depolymerization is frequently applied to lignin to generate phenolic monomers. However, due to the instability of phenolic intermediates, repol...

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Autores principales: Liu, Mingyang, Dyson, Paul J.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Nature Publishing Group UK 2023
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10203214/
https://www.ncbi.nlm.nih.gov/pubmed/37217549
http://dx.doi.org/10.1038/s41467-023-38534-1
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author Liu, Mingyang
Dyson, Paul J.
author_facet Liu, Mingyang
Dyson, Paul J.
author_sort Liu, Mingyang
collection PubMed
description Efficient valorization of lignin, a sustainable source of functionalized aromatic products, would reduce dependence on fossil-derived feedstocks. Oxidative depolymerization is frequently applied to lignin to generate phenolic monomers. However, due to the instability of phenolic intermediates, repolymerization and dearylation reactions lead to low selectivity and product yields. Here, a highly efficient strategy to extract the aromatic monomers from lignin affording functionalized diaryl ethers using oxidative cross-coupling reactions is described, which overcomes the limitations of oxidative methods and affords high-value specialty chemicals. Reaction of phenylboronic acids with lignin converts the reactive phenolic intermediates into stable diaryl ether products in near-theoretical maximum yields (92% for beech lignin and 95% for poplar lignin based on the content of β−O−4 linkages). This strategy suppresses side reactions typically encountered in oxidative depolymerization reactions of lignin and provides a new approach for the direct transformation of lignin into valuable functionalized diaryl ethers, including key intermediates in pharmaceutical and natural product synthesis.
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spelling pubmed-102032142023-05-24 Direct conversion of lignin to functionalized diaryl ethers via oxidative cross-coupling Liu, Mingyang Dyson, Paul J. Nat Commun Article Efficient valorization of lignin, a sustainable source of functionalized aromatic products, would reduce dependence on fossil-derived feedstocks. Oxidative depolymerization is frequently applied to lignin to generate phenolic monomers. However, due to the instability of phenolic intermediates, repolymerization and dearylation reactions lead to low selectivity and product yields. Here, a highly efficient strategy to extract the aromatic monomers from lignin affording functionalized diaryl ethers using oxidative cross-coupling reactions is described, which overcomes the limitations of oxidative methods and affords high-value specialty chemicals. Reaction of phenylboronic acids with lignin converts the reactive phenolic intermediates into stable diaryl ether products in near-theoretical maximum yields (92% for beech lignin and 95% for poplar lignin based on the content of β−O−4 linkages). This strategy suppresses side reactions typically encountered in oxidative depolymerization reactions of lignin and provides a new approach for the direct transformation of lignin into valuable functionalized diaryl ethers, including key intermediates in pharmaceutical and natural product synthesis. Nature Publishing Group UK 2023-05-22 /pmc/articles/PMC10203214/ /pubmed/37217549 http://dx.doi.org/10.1038/s41467-023-38534-1 Text en © The Author(s) 2023 https://creativecommons.org/licenses/by/4.0/Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/ (https://creativecommons.org/licenses/by/4.0/) .
spellingShingle Article
Liu, Mingyang
Dyson, Paul J.
Direct conversion of lignin to functionalized diaryl ethers via oxidative cross-coupling
title Direct conversion of lignin to functionalized diaryl ethers via oxidative cross-coupling
title_full Direct conversion of lignin to functionalized diaryl ethers via oxidative cross-coupling
title_fullStr Direct conversion of lignin to functionalized diaryl ethers via oxidative cross-coupling
title_full_unstemmed Direct conversion of lignin to functionalized diaryl ethers via oxidative cross-coupling
title_short Direct conversion of lignin to functionalized diaryl ethers via oxidative cross-coupling
title_sort direct conversion of lignin to functionalized diaryl ethers via oxidative cross-coupling
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10203214/
https://www.ncbi.nlm.nih.gov/pubmed/37217549
http://dx.doi.org/10.1038/s41467-023-38534-1
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