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Ligandless Palladium-Catalyzed Direct C-5 Arylation of Azoles Promoted by Benzoic Acid in Anisole

The palladium-catalyzed direct arylation of azoles with (hetero)aryl halides is nowadays one of the most versatile and efficient procedures for the selective synthesis of heterobiaryls. Although this procedure is, due to its characteristics, also of great interest in the industrial field, the wide u...

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Autores principales: Rosadoni, Elisabetta, Banchini, Federico, Bellini, Sara, Lessi, Marco, Pasquinelli, Luca, Bellina, Fabio
Formato: Online Artículo Texto
Lenguaje:English
Publicado: MDPI 2022
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9735507/
https://www.ncbi.nlm.nih.gov/pubmed/36500546
http://dx.doi.org/10.3390/molecules27238454
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author Rosadoni, Elisabetta
Banchini, Federico
Bellini, Sara
Lessi, Marco
Pasquinelli, Luca
Bellina, Fabio
author_facet Rosadoni, Elisabetta
Banchini, Federico
Bellini, Sara
Lessi, Marco
Pasquinelli, Luca
Bellina, Fabio
author_sort Rosadoni, Elisabetta
collection PubMed
description The palladium-catalyzed direct arylation of azoles with (hetero)aryl halides is nowadays one of the most versatile and efficient procedures for the selective synthesis of heterobiaryls. Although this procedure is, due to its characteristics, also of great interest in the industrial field, the wide use of a reaction medium such as DMF or DMA, two polar aprotic solvents coded as dangerous according to environmental, health, safety (EHS) parameters, strongly limits its actual use. In contrast, the use of aromatic solvents as the reaction medium for direct arylations, although some of them show good EHS values, is poorly reported, probably due to their low solvent power against reagents and their potential involvement in undesired side reactions. In this paper we report an unprecedented selective C-5 arylation procedure involving anisole as an EHS green reaction solvent. In addition, the beneficial role of benzoic acid as an additive was also highlighted, a role that had never been previously described.
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spelling pubmed-97355072022-12-11 Ligandless Palladium-Catalyzed Direct C-5 Arylation of Azoles Promoted by Benzoic Acid in Anisole Rosadoni, Elisabetta Banchini, Federico Bellini, Sara Lessi, Marco Pasquinelli, Luca Bellina, Fabio Molecules Article The palladium-catalyzed direct arylation of azoles with (hetero)aryl halides is nowadays one of the most versatile and efficient procedures for the selective synthesis of heterobiaryls. Although this procedure is, due to its characteristics, also of great interest in the industrial field, the wide use of a reaction medium such as DMF or DMA, two polar aprotic solvents coded as dangerous according to environmental, health, safety (EHS) parameters, strongly limits its actual use. In contrast, the use of aromatic solvents as the reaction medium for direct arylations, although some of them show good EHS values, is poorly reported, probably due to their low solvent power against reagents and their potential involvement in undesired side reactions. In this paper we report an unprecedented selective C-5 arylation procedure involving anisole as an EHS green reaction solvent. In addition, the beneficial role of benzoic acid as an additive was also highlighted, a role that had never been previously described. MDPI 2022-12-02 /pmc/articles/PMC9735507/ /pubmed/36500546 http://dx.doi.org/10.3390/molecules27238454 Text en © 2022 by the authors. https://creativecommons.org/licenses/by/4.0/Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https://creativecommons.org/licenses/by/4.0/).
spellingShingle Article
Rosadoni, Elisabetta
Banchini, Federico
Bellini, Sara
Lessi, Marco
Pasquinelli, Luca
Bellina, Fabio
Ligandless Palladium-Catalyzed Direct C-5 Arylation of Azoles Promoted by Benzoic Acid in Anisole
title Ligandless Palladium-Catalyzed Direct C-5 Arylation of Azoles Promoted by Benzoic Acid in Anisole
title_full Ligandless Palladium-Catalyzed Direct C-5 Arylation of Azoles Promoted by Benzoic Acid in Anisole
title_fullStr Ligandless Palladium-Catalyzed Direct C-5 Arylation of Azoles Promoted by Benzoic Acid in Anisole
title_full_unstemmed Ligandless Palladium-Catalyzed Direct C-5 Arylation of Azoles Promoted by Benzoic Acid in Anisole
title_short Ligandless Palladium-Catalyzed Direct C-5 Arylation of Azoles Promoted by Benzoic Acid in Anisole
title_sort ligandless palladium-catalyzed direct c-5 arylation of azoles promoted by benzoic acid in anisole
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9735507/
https://www.ncbi.nlm.nih.gov/pubmed/36500546
http://dx.doi.org/10.3390/molecules27238454
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