Understanding the Regiodivergence between Hydroarylation and Trifluoromethylarylation of 1,3-Dienes Using Anilines in HFIP

Conjugated dienes (1,3-dienes) are versatile and valuable chemical feedstocks that can be used as two-carbon or four-carbon synthons with vast applications across the chemical industry. However, the main challenge for their productive incorporation in synthetic routes is their chemo-, regio-, and st...

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Detalles Bibliográficos
Autores: Corral Suarez, C., Fernández, Israel, Colomer, Ignacio
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2024
País:España
Institución:Consejo Superior de Investigaciones Científicas (CSIC)
Repositorio:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/367150
Acceso en línea:http://hdl.handle.net/10261/367150
Access Level:acceso abierto
Palabra clave:arylation
trifluoromethyl
diene
aniline
regiodivergence
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spelling Understanding the Regiodivergence between Hydroarylation and Trifluoromethylarylation of 1,3-Dienes Using Anilines in HFIPCorral Suarez, C.Fernández, IsraelColomer, IgnacioarylationtrifluoromethyldieneanilineregiodivergenceConjugated dienes (1,3-dienes) are versatile and valuable chemical feedstocks that can be used as two-carbon or four-carbon synthons with vast applications across the chemical industry. However, the main challenge for their productive incorporation in synthetic routes is their chemo-, regio-, and stereoselective functionalization. Herein, we introduce a unified strategy for the 1,2-hydroarylation and 1,4-trifluoromethylarylation of 1,3-dienes using anilines in hexafluoroisopropanol. DFT calculations point toward a kinetically controlled process in both transformations, particularly in the trifluoromethylarylation, to explain the regiodivergent outcome. In addition, we perform an extensive program of functionalization and diversification of the products obtained, including hydrogenation, oxidation, cyclizations, or cross-coupling reactions, that allows access to a library of high-value species in a straightforward manner.We acknowledge funding from the Spanish MCIN/AEI/ 10.13039/501100011033 (RyC2019-026674-I and PID2022- 141911NB-I00 to I.C. and PID2019-106184GB-I00, PID2022- 139318NB-I00, and RED2022-134287-T to I.F.) and CSIC (PIE 20218AT015 and PIE 202280I025 to I.C.). We thank Eugenio Millán and María Vera for providing dienes, Gonzalo Dorado for preliminary hydroarylation experiments, and Dr. Josefina Perles (UAM) for performing X-ray structure analysis.Peer reviewedACS PublicationsMinisterio de Ciencia, Innovación y Universidades (España)Consejo Superior de Investigaciones Científicas (España)Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]2024202420242024info:eu-repo/semantics/articlehttp://purl.org/coar/resource_type/c_6501Publisher's versioninfo:eu-repo/semantics/publishedVersionhttp://hdl.handle.net/10261/367150reponame:DIGITAL.CSIC. Repositorio Institucional del CSICinstname:Consejo Superior de Investigaciones Científicas (CSIC)Inglés#PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE#info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023/PID2022-141911NB-I00info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PID2019-106184GB-I00info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023/PID2022-139318NB-I00http://dx.doi.org/10.1021/jacsau.4c00162Síinfo:eu-repo/semantics/openAccessoai:digital.csic.es:10261/3671502026-05-22T06:33:51Z
dc.title.none.fl_str_mv Understanding the Regiodivergence between Hydroarylation and Trifluoromethylarylation of 1,3-Dienes Using Anilines in HFIP
title Understanding the Regiodivergence between Hydroarylation and Trifluoromethylarylation of 1,3-Dienes Using Anilines in HFIP
spellingShingle Understanding the Regiodivergence between Hydroarylation and Trifluoromethylarylation of 1,3-Dienes Using Anilines in HFIP
Corral Suarez, C.
arylation
trifluoromethyl
diene
aniline
regiodivergence
title_short Understanding the Regiodivergence between Hydroarylation and Trifluoromethylarylation of 1,3-Dienes Using Anilines in HFIP
title_full Understanding the Regiodivergence between Hydroarylation and Trifluoromethylarylation of 1,3-Dienes Using Anilines in HFIP
title_fullStr Understanding the Regiodivergence between Hydroarylation and Trifluoromethylarylation of 1,3-Dienes Using Anilines in HFIP
title_full_unstemmed Understanding the Regiodivergence between Hydroarylation and Trifluoromethylarylation of 1,3-Dienes Using Anilines in HFIP
title_sort Understanding the Regiodivergence between Hydroarylation and Trifluoromethylarylation of 1,3-Dienes Using Anilines in HFIP
dc.creator.none.fl_str_mv Corral Suarez, C.
Fernández, Israel
Colomer, Ignacio
author Corral Suarez, C.
author_facet Corral Suarez, C.
Fernández, Israel
Colomer, Ignacio
author_role author
author2 Fernández, Israel
Colomer, Ignacio
author2_role author
author
dc.contributor.none.fl_str_mv Ministerio de Ciencia, Innovación y Universidades (España)
Consejo Superior de Investigaciones Científicas (España)
Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]
dc.subject.none.fl_str_mv arylation
trifluoromethyl
diene
aniline
regiodivergence
topic arylation
trifluoromethyl
diene
aniline
regiodivergence
description Conjugated dienes (1,3-dienes) are versatile and valuable chemical feedstocks that can be used as two-carbon or four-carbon synthons with vast applications across the chemical industry. However, the main challenge for their productive incorporation in synthetic routes is their chemo-, regio-, and stereoselective functionalization. Herein, we introduce a unified strategy for the 1,2-hydroarylation and 1,4-trifluoromethylarylation of 1,3-dienes using anilines in hexafluoroisopropanol. DFT calculations point toward a kinetically controlled process in both transformations, particularly in the trifluoromethylarylation, to explain the regiodivergent outcome. In addition, we perform an extensive program of functionalization and diversification of the products obtained, including hydrogenation, oxidation, cyclizations, or cross-coupling reactions, that allows access to a library of high-value species in a straightforward manner.
publishDate 2024
dc.date.none.fl_str_mv 2024
2024
2024
2024
dc.type.none.fl_str_mv info:eu-repo/semantics/article
http://purl.org/coar/resource_type/c_6501
Publisher's version
info:eu-repo/semantics/publishedVersion
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/10261/367150
url http://hdl.handle.net/10261/367150
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv #PLACEHOLDER_PARENT_METADATA_VALUE#
#PLACEHOLDER_PARENT_METADATA_VALUE#
#PLACEHOLDER_PARENT_METADATA_VALUE#
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023/PID2022-141911NB-I00
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PID2019-106184GB-I00
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023/PID2022-139318NB-I00
http://dx.doi.org/10.1021/jacsau.4c00162
Sí
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.publisher.none.fl_str_mv ACS Publications
publisher.none.fl_str_mv ACS Publications
dc.source.none.fl_str_mv reponame:DIGITAL.CSIC. Repositorio Institucional del CSIC
instname:Consejo Superior de Investigaciones Científicas (CSIC)
instname_str Consejo Superior de Investigaciones Científicas (CSIC)
reponame_str DIGITAL.CSIC. Repositorio Institucional del CSIC
collection DIGITAL.CSIC. Repositorio Institucional del CSIC
repository.name.fl_str_mv
repository.mail.fl_str_mv
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