Mechanism of Gold-Catalyzed Arylation-Lactonization: A Density Functional Theory Study on the Role of the (MIC^N)AuCl Complex in Au(I)/Au(III) Catalysis

Gold-catalyzed redox transformations via Au(I)/Au(III) cycles offer efficient oxidative addition and reductive elimination under mild, oxidant-free conditions. Recent studies highlight the role of hemilabile mesoionic carbene (MIC) ligands in stabilizing key intermediates. Using DFT, we investigated...

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Autores: Monreal Corona, Roger, Ribas Salamaña, Xavi, Pla i Quintana, Anna, Poater Teixidor, Albert
Formato: artículo
Estado:Versión publicada
Fecha de publicación:2025
País:España
Recursos:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
Repositorio:Recercat. Dipósit de la Recerca de Catalunya
OAI Identifier:oai:recercat.cat:10256/27220
Acesso em linha:http://hdl.handle.net/10256/27220
Access Level:acceso abierto
Palavra-chave:Anions
Catalitzadors
Catalysts
Lligands
Ligands
Reaccions químiques orgàniques -- Mecanismes
Organic reaction mechanisms
Reaccions d'addició
Addition reactions
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spelling Mechanism of Gold-Catalyzed Arylation-Lactonization: A Density Functional Theory Study on the Role of the (MIC^N)AuCl Complex in Au(I)/Au(III) CatalysisMonreal Corona, RogerRibas Salamaña, XaviPla i Quintana, AnnaPoater Teixidor, AlbertAnionsCatalitzadorsCatalystsLligandsLigandsReaccions químiques orgàniques -- MecanismesOrganic reaction mechanismsReaccions d'addicióAddition reactionsGold-catalyzed redox transformations via Au(I)/Au(III) cycles offer efficient oxidative addition and reductive elimination under mild, oxidant-free conditions. Recent studies highlight the role of hemilabile mesoionic carbene (MIC) ligands in stabilizing key intermediates. Using DFT, we investigated the mechanism of the arylation-lactonization of γ-alkenoic acids, revealing two viable pathways, cis and trans, each with distinct rate-determining steps. While the trans pathway avoids decomposition of the catalyst, its lactonization step is hindered by a high barrier. In contrast, the cis pathway features competing productive and decomposition routes. By correlating computed activation barriers with experimental yields, we built statistically significant multivariable models (R2 = 0.919), enabling the prediction of product yields across various substituted aryl iodides. These models revealed clear electronic and steric trends. Additionally, ligand modifications suggest that trans-selective oxidative addition can be improved through steric tuning with the trans effect also influencing selectivity. Overall, this study provides valuable design principles for future gold-catalyzed redox processesWe are grateful for financial support from the Ministerio de Ciencia e Innovación (PID2021-127423NB-I00, PID2022-136970NB-I00, TED2021-130573B-100, and PID2023-146849NB I00/MICIU/AEI/10.13039/501100011033/FEDER, UE projects) and the Generalitat de Catalunya (2021-SGR-623 and 2021 SGR 00475). We thank the Spanish Ministerio de Universidades for the predoctoral fellowship FPU20/00707 to R.M.-C. A.P.-Q. and A.P. are Serra Húnter Fellows, and X.R. thanks ICREA Academia Prize 2020American Chemical Society (ACS)Agencia Estatal de Investigación2025info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionpeer-reviewedapplication/pdfhttp://hdl.handle.net/10256/27220Inorganic Chemistry, 2025, vol. 64, núm. 25, p. 12755-12761Articles publicats (D-Q)reponame:Recercat. Dipósit de la Recerca de Catalunyainstname:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)Inglésinfo:eu-repo/semantics/altIdentifier/doi/10.1021/acs.inorgchem.5c01666info:eu-repo/semantics/altIdentifier/issn/0020-1669info:eu-repo/semantics/altIdentifier/eissn/1520-510XPID2021-127423NB-I00PID2022-136970NB-I00PID2023-146849NB-I00info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023/PID2021-127423NB-I00info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023/PID2022-136970NB-I00info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023/PID2023-146849NB-I00Attribution 4.0 Internationalhttp://creativecommons.org/licenses/by/4.0/info:eu-repo/semantics/openAccessoai:recercat.cat:10256/272202026-05-29T05:05:01Z
dc.title.none.fl_str_mv Mechanism of Gold-Catalyzed Arylation-Lactonization: A Density Functional Theory Study on the Role of the (MIC^N)AuCl Complex in Au(I)/Au(III) Catalysis
title Mechanism of Gold-Catalyzed Arylation-Lactonization: A Density Functional Theory Study on the Role of the (MIC^N)AuCl Complex in Au(I)/Au(III) Catalysis
spellingShingle Mechanism of Gold-Catalyzed Arylation-Lactonization: A Density Functional Theory Study on the Role of the (MIC^N)AuCl Complex in Au(I)/Au(III) Catalysis
Monreal Corona, Roger
Anions
Catalitzadors
Catalysts
Lligands
Ligands
Reaccions químiques orgàniques -- Mecanismes
Organic reaction mechanisms
Reaccions d'addició
Addition reactions
title_short Mechanism of Gold-Catalyzed Arylation-Lactonization: A Density Functional Theory Study on the Role of the (MIC^N)AuCl Complex in Au(I)/Au(III) Catalysis
title_full Mechanism of Gold-Catalyzed Arylation-Lactonization: A Density Functional Theory Study on the Role of the (MIC^N)AuCl Complex in Au(I)/Au(III) Catalysis
title_fullStr Mechanism of Gold-Catalyzed Arylation-Lactonization: A Density Functional Theory Study on the Role of the (MIC^N)AuCl Complex in Au(I)/Au(III) Catalysis
title_full_unstemmed Mechanism of Gold-Catalyzed Arylation-Lactonization: A Density Functional Theory Study on the Role of the (MIC^N)AuCl Complex in Au(I)/Au(III) Catalysis
title_sort Mechanism of Gold-Catalyzed Arylation-Lactonization: A Density Functional Theory Study on the Role of the (MIC^N)AuCl Complex in Au(I)/Au(III) Catalysis
dc.creator.none.fl_str_mv Monreal Corona, Roger
Ribas Salamaña, Xavi
Pla i Quintana, Anna
Poater Teixidor, Albert
author Monreal Corona, Roger
author_facet Monreal Corona, Roger
Ribas Salamaña, Xavi
Pla i Quintana, Anna
Poater Teixidor, Albert
author_role author
author2 Ribas Salamaña, Xavi
Pla i Quintana, Anna
Poater Teixidor, Albert
author2_role author
author
author
dc.contributor.none.fl_str_mv Agencia Estatal de Investigación
dc.subject.none.fl_str_mv Anions
Catalitzadors
Catalysts
Lligands
Ligands
Reaccions químiques orgàniques -- Mecanismes
Organic reaction mechanisms
Reaccions d'addició
Addition reactions
topic Anions
Catalitzadors
Catalysts
Lligands
Ligands
Reaccions químiques orgàniques -- Mecanismes
Organic reaction mechanisms
Reaccions d'addició
Addition reactions
description Gold-catalyzed redox transformations via Au(I)/Au(III) cycles offer efficient oxidative addition and reductive elimination under mild, oxidant-free conditions. Recent studies highlight the role of hemilabile mesoionic carbene (MIC) ligands in stabilizing key intermediates. Using DFT, we investigated the mechanism of the arylation-lactonization of γ-alkenoic acids, revealing two viable pathways, cis and trans, each with distinct rate-determining steps. While the trans pathway avoids decomposition of the catalyst, its lactonization step is hindered by a high barrier. In contrast, the cis pathway features competing productive and decomposition routes. By correlating computed activation barriers with experimental yields, we built statistically significant multivariable models (R2 = 0.919), enabling the prediction of product yields across various substituted aryl iodides. These models revealed clear electronic and steric trends. Additionally, ligand modifications suggest that trans-selective oxidative addition can be improved through steric tuning with the trans effect also influencing selectivity. Overall, this study provides valuable design principles for future gold-catalyzed redox processes
publishDate 2025
dc.date.none.fl_str_mv 2025
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
peer-reviewed
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/10256/27220
url http://hdl.handle.net/10256/27220
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1021/acs.inorgchem.5c01666
info:eu-repo/semantics/altIdentifier/issn/0020-1669
info:eu-repo/semantics/altIdentifier/eissn/1520-510X
PID2021-127423NB-I00
PID2022-136970NB-I00
PID2023-146849NB-I00
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023/PID2021-127423NB-I00
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023/PID2022-136970NB-I00
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023/PID2023-146849NB-I00
dc.rights.none.fl_str_mv Attribution 4.0 International
http://creativecommons.org/licenses/by/4.0/
info:eu-repo/semantics/openAccess
rights_invalid_str_mv Attribution 4.0 International
http://creativecommons.org/licenses/by/4.0/
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv American Chemical Society (ACS)
publisher.none.fl_str_mv American Chemical Society (ACS)
dc.source.none.fl_str_mv Inorganic Chemistry, 2025, vol. 64, núm. 25, p. 12755-12761
Articles publicats (D-Q)
reponame:Recercat. Dipósit de la Recerca de Catalunya
instname:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
instname_str Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
reponame_str Recercat. Dipósit de la Recerca de Catalunya
collection Recercat. Dipósit de la Recerca de Catalunya
repository.name.fl_str_mv
repository.mail.fl_str_mv
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score 15,812429

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