Cargando…
Visible-light photoredox-catalyzed C–O bond cleavage of diaryl ethers by acridinium photocatalysts at room temperature
Cleavage of C–O bonds in lignin can afford the renewable aryl sources for fine chemicals. However, the high bond energies of these C–O bonds, especially the 4-O-5-type diaryl ether C–O bonds (~314 kJ/mol) make the cleavage very challenging. Here, we report visible-light photoredox-catalyzed C–O bond...
Autores principales: | , , , |
---|---|
Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
Nature Publishing Group UK
2020
|
Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7705023/ https://www.ncbi.nlm.nih.gov/pubmed/33257656 http://dx.doi.org/10.1038/s41467-020-19944-x |
_version_ | 1783616876994101248 |
---|---|
author | Tan, Fang-Fang He, Xiao-Ya Tian, Wan-Fa Li, Yang |
author_facet | Tan, Fang-Fang He, Xiao-Ya Tian, Wan-Fa Li, Yang |
author_sort | Tan, Fang-Fang |
collection | PubMed |
description | Cleavage of C–O bonds in lignin can afford the renewable aryl sources for fine chemicals. However, the high bond energies of these C–O bonds, especially the 4-O-5-type diaryl ether C–O bonds (~314 kJ/mol) make the cleavage very challenging. Here, we report visible-light photoredox-catalyzed C–O bond cleavage of diaryl ethers by an acidolysis with an aryl carboxylic acid and a following one-pot hydrolysis. Two molecules of phenols are obtained from one molecule of diaryl ether at room temperature. The aryl carboxylic acid used for the acidolysis can be recovered. The key to success of the acidolysis is merging visible-light photoredox catalysis using an acridinium photocatalyst and Lewis acid catalysis using Cu(TMHD)(2). Preliminary mechanistic studies indicate that the catalytic cycle occurs via a rare selective electrophilic attack of the generated aryl carboxylic radical on the electron-rich aryl ring of the diphenyl ether. This transformation is applied to a gram-scale reaction and the model of 4-O-5 lignin linkages. |
format | Online Article Text |
id | pubmed-7705023 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2020 |
publisher | Nature Publishing Group UK |
record_format | MEDLINE/PubMed |
spelling | pubmed-77050232020-12-03 Visible-light photoredox-catalyzed C–O bond cleavage of diaryl ethers by acridinium photocatalysts at room temperature Tan, Fang-Fang He, Xiao-Ya Tian, Wan-Fa Li, Yang Nat Commun Article Cleavage of C–O bonds in lignin can afford the renewable aryl sources for fine chemicals. However, the high bond energies of these C–O bonds, especially the 4-O-5-type diaryl ether C–O bonds (~314 kJ/mol) make the cleavage very challenging. Here, we report visible-light photoredox-catalyzed C–O bond cleavage of diaryl ethers by an acidolysis with an aryl carboxylic acid and a following one-pot hydrolysis. Two molecules of phenols are obtained from one molecule of diaryl ether at room temperature. The aryl carboxylic acid used for the acidolysis can be recovered. The key to success of the acidolysis is merging visible-light photoredox catalysis using an acridinium photocatalyst and Lewis acid catalysis using Cu(TMHD)(2). Preliminary mechanistic studies indicate that the catalytic cycle occurs via a rare selective electrophilic attack of the generated aryl carboxylic radical on the electron-rich aryl ring of the diphenyl ether. This transformation is applied to a gram-scale reaction and the model of 4-O-5 lignin linkages. Nature Publishing Group UK 2020-11-30 /pmc/articles/PMC7705023/ /pubmed/33257656 http://dx.doi.org/10.1038/s41467-020-19944-x Text en © The Author(s) 2020 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/. |
spellingShingle | Article Tan, Fang-Fang He, Xiao-Ya Tian, Wan-Fa Li, Yang Visible-light photoredox-catalyzed C–O bond cleavage of diaryl ethers by acridinium photocatalysts at room temperature |
title | Visible-light photoredox-catalyzed C–O bond cleavage of diaryl ethers by acridinium photocatalysts at room temperature |
title_full | Visible-light photoredox-catalyzed C–O bond cleavage of diaryl ethers by acridinium photocatalysts at room temperature |
title_fullStr | Visible-light photoredox-catalyzed C–O bond cleavage of diaryl ethers by acridinium photocatalysts at room temperature |
title_full_unstemmed | Visible-light photoredox-catalyzed C–O bond cleavage of diaryl ethers by acridinium photocatalysts at room temperature |
title_short | Visible-light photoredox-catalyzed C–O bond cleavage of diaryl ethers by acridinium photocatalysts at room temperature |
title_sort | visible-light photoredox-catalyzed c–o bond cleavage of diaryl ethers by acridinium photocatalysts at room temperature |
topic | Article |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7705023/ https://www.ncbi.nlm.nih.gov/pubmed/33257656 http://dx.doi.org/10.1038/s41467-020-19944-x |
work_keys_str_mv | AT tanfangfang visiblelightphotoredoxcatalyzedcobondcleavageofdiarylethersbyacridiniumphotocatalystsatroomtemperature AT hexiaoya visiblelightphotoredoxcatalyzedcobondcleavageofdiarylethersbyacridiniumphotocatalystsatroomtemperature AT tianwanfa visiblelightphotoredoxcatalyzedcobondcleavageofdiarylethersbyacridiniumphotocatalystsatroomtemperature AT liyang visiblelightphotoredoxcatalyzedcobondcleavageofdiarylethersbyacridiniumphotocatalystsatroomtemperature |