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Mechanistic studies of the palladium-catalyzed S,O-ligand promoted C–H olefination of aromatic compounds
Pd-catalyzed C–H functionalization reactions of non-directed substrates have recently emerged as an attractive alternative to the use of directing groups. Key to the success of these transformations has been the discovery of new ligands capable of increasing both the reactivity of the inert C–H bond...
Autores principales: | , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
The Royal Society of Chemistry
2023
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10016329/ https://www.ncbi.nlm.nih.gov/pubmed/36937590 http://dx.doi.org/10.1039/d2sc06840k |
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author | Naksomboon, Kananat Gómez-Bengoa, Enrique Mehara, Jaya Roithová, Jana Otten, Edwin Fernández-Ibáñez, M. Ángeles |
author_facet | Naksomboon, Kananat Gómez-Bengoa, Enrique Mehara, Jaya Roithová, Jana Otten, Edwin Fernández-Ibáñez, M. Ángeles |
author_sort | Naksomboon, Kananat |
collection | PubMed |
description | Pd-catalyzed C–H functionalization reactions of non-directed substrates have recently emerged as an attractive alternative to the use of directing groups. Key to the success of these transformations has been the discovery of new ligands capable of increasing both the reactivity of the inert C–H bond and the selectivity of the process. Among them, a new type of S,O-ligand has been shown to be highly efficient in promoting a variety of Pd-catalyzed C–H olefination reactions of non-directed arenes. Despite the success of this type of S,O-ligand, its role in the C–H functionalization processes is unknown. Herein, we describe a detailed mechanistic study focused on elucidating the role of the S,O-ligand in the Pd-catalyzed C–H olefination of non-directed arenes. For this purpose, several mechanistic tools, including isolation and characterization of reactive intermediates, NMR and kinetic studies, isotope effects and DFT calculations have been employed. The data from these experiments suggest that the C–H activation is the rate-determining step in both cases with and without the S,O-ligand. Furthermore, the results indicate that the S,O-ligand triggers the formation of more reactive Pd cationic species, which explains the observed acceleration of the reaction. Together, these studies shed light on the role of the S,O-ligand in promoting Pd-catalyzed C–H functionalization reactions. |
format | Online Article Text |
id | pubmed-10016329 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2023 |
publisher | The Royal Society of Chemistry |
record_format | MEDLINE/PubMed |
spelling | pubmed-100163292023-03-16 Mechanistic studies of the palladium-catalyzed S,O-ligand promoted C–H olefination of aromatic compounds Naksomboon, Kananat Gómez-Bengoa, Enrique Mehara, Jaya Roithová, Jana Otten, Edwin Fernández-Ibáñez, M. Ángeles Chem Sci Chemistry Pd-catalyzed C–H functionalization reactions of non-directed substrates have recently emerged as an attractive alternative to the use of directing groups. Key to the success of these transformations has been the discovery of new ligands capable of increasing both the reactivity of the inert C–H bond and the selectivity of the process. Among them, a new type of S,O-ligand has been shown to be highly efficient in promoting a variety of Pd-catalyzed C–H olefination reactions of non-directed arenes. Despite the success of this type of S,O-ligand, its role in the C–H functionalization processes is unknown. Herein, we describe a detailed mechanistic study focused on elucidating the role of the S,O-ligand in the Pd-catalyzed C–H olefination of non-directed arenes. For this purpose, several mechanistic tools, including isolation and characterization of reactive intermediates, NMR and kinetic studies, isotope effects and DFT calculations have been employed. The data from these experiments suggest that the C–H activation is the rate-determining step in both cases with and without the S,O-ligand. Furthermore, the results indicate that the S,O-ligand triggers the formation of more reactive Pd cationic species, which explains the observed acceleration of the reaction. Together, these studies shed light on the role of the S,O-ligand in promoting Pd-catalyzed C–H functionalization reactions. The Royal Society of Chemistry 2023-02-16 /pmc/articles/PMC10016329/ /pubmed/36937590 http://dx.doi.org/10.1039/d2sc06840k Text en This journal is © The Royal Society of Chemistry https://creativecommons.org/licenses/by/3.0/ |
spellingShingle | Chemistry Naksomboon, Kananat Gómez-Bengoa, Enrique Mehara, Jaya Roithová, Jana Otten, Edwin Fernández-Ibáñez, M. Ángeles Mechanistic studies of the palladium-catalyzed S,O-ligand promoted C–H olefination of aromatic compounds |
title | Mechanistic studies of the palladium-catalyzed S,O-ligand promoted C–H olefination of aromatic compounds |
title_full | Mechanistic studies of the palladium-catalyzed S,O-ligand promoted C–H olefination of aromatic compounds |
title_fullStr | Mechanistic studies of the palladium-catalyzed S,O-ligand promoted C–H olefination of aromatic compounds |
title_full_unstemmed | Mechanistic studies of the palladium-catalyzed S,O-ligand promoted C–H olefination of aromatic compounds |
title_short | Mechanistic studies of the palladium-catalyzed S,O-ligand promoted C–H olefination of aromatic compounds |
title_sort | mechanistic studies of the palladium-catalyzed s,o-ligand promoted c–h olefination of aromatic compounds |
topic | Chemistry |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10016329/ https://www.ncbi.nlm.nih.gov/pubmed/36937590 http://dx.doi.org/10.1039/d2sc06840k |
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