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Unified synthesis of mono/bis-arylated phenols via Rh(III)-catalyzed dehydrogenative coupling

2,6-Bis-arylated phenols are rarely reported and are synthetically challenging. Directed C–H functionalization reactions, using a directing group (DG), might provide a convenient solution to their synthesis. However, this strategy usually results in partial cleavage of the directing group, preventin...

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Autores principales: Wu, Qian, Chen, Ying, Yan, Dingyuan, Zhang, Muyue, Lu, Yi, Sun, Wei-Yin, Zhao, Jing
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Royal Society of Chemistry 2017
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5308286/
https://www.ncbi.nlm.nih.gov/pubmed/28451162
http://dx.doi.org/10.1039/c6sc03169b
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author Wu, Qian
Chen, Ying
Yan, Dingyuan
Zhang, Muyue
Lu, Yi
Sun, Wei-Yin
Zhao, Jing
author_facet Wu, Qian
Chen, Ying
Yan, Dingyuan
Zhang, Muyue
Lu, Yi
Sun, Wei-Yin
Zhao, Jing
author_sort Wu, Qian
collection PubMed
description 2,6-Bis-arylated phenols are rarely reported and are synthetically challenging. Directed C–H functionalization reactions, using a directing group (DG), might provide a convenient solution to their synthesis. However, this strategy usually results in partial cleavage of the directing group, preventing further/second C–H activation cascades. Herein we report a general strategy that allows for the precise control of the oxidation pathways so that directing groups can be either preserved or cleaved. We found that N-phenoxyacetamides could undergo ortho-arylation reactions with or without an external oxidant, yielding products with different oxidation states, notably the rare bis-arylated phenols. Notably, a unique rhodacycle intermediate was isolated, characterized by X-ray crystallography, and confirmed to be an active catalyst. Switching between internal and external oxidation could be a general strategy in diverse directed C–H functionalization reactions to realize bis-functionalized products.
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spelling pubmed-53082862017-04-27 Unified synthesis of mono/bis-arylated phenols via Rh(III)-catalyzed dehydrogenative coupling Wu, Qian Chen, Ying Yan, Dingyuan Zhang, Muyue Lu, Yi Sun, Wei-Yin Zhao, Jing Chem Sci Chemistry 2,6-Bis-arylated phenols are rarely reported and are synthetically challenging. Directed C–H functionalization reactions, using a directing group (DG), might provide a convenient solution to their synthesis. However, this strategy usually results in partial cleavage of the directing group, preventing further/second C–H activation cascades. Herein we report a general strategy that allows for the precise control of the oxidation pathways so that directing groups can be either preserved or cleaved. We found that N-phenoxyacetamides could undergo ortho-arylation reactions with or without an external oxidant, yielding products with different oxidation states, notably the rare bis-arylated phenols. Notably, a unique rhodacycle intermediate was isolated, characterized by X-ray crystallography, and confirmed to be an active catalyst. Switching between internal and external oxidation could be a general strategy in diverse directed C–H functionalization reactions to realize bis-functionalized products. Royal Society of Chemistry 2017-01-01 2016-08-03 /pmc/articles/PMC5308286/ /pubmed/28451162 http://dx.doi.org/10.1039/c6sc03169b Text en This journal is © The Royal Society of Chemistry 2016 http://creativecommons.org/licenses/by/3.0/ This is an Open Access article distributed under the terms of the Creative Commons Attribution 3.0 Unported License (http://creativecommons.org/licenses/by/3.0/) which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
spellingShingle Chemistry
Wu, Qian
Chen, Ying
Yan, Dingyuan
Zhang, Muyue
Lu, Yi
Sun, Wei-Yin
Zhao, Jing
Unified synthesis of mono/bis-arylated phenols via Rh(III)-catalyzed dehydrogenative coupling
title Unified synthesis of mono/bis-arylated phenols via Rh(III)-catalyzed dehydrogenative coupling
title_full Unified synthesis of mono/bis-arylated phenols via Rh(III)-catalyzed dehydrogenative coupling
title_fullStr Unified synthesis of mono/bis-arylated phenols via Rh(III)-catalyzed dehydrogenative coupling
title_full_unstemmed Unified synthesis of mono/bis-arylated phenols via Rh(III)-catalyzed dehydrogenative coupling
title_short Unified synthesis of mono/bis-arylated phenols via Rh(III)-catalyzed dehydrogenative coupling
title_sort unified synthesis of mono/bis-arylated phenols via rh(iii)-catalyzed dehydrogenative coupling
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5308286/
https://www.ncbi.nlm.nih.gov/pubmed/28451162
http://dx.doi.org/10.1039/c6sc03169b
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