Dynamic Kinetic Resolution of Indole-Based Sulfenylated Heterobiaryls by Rhodium-Catalyzed Atroposelective Reductive Aldol Reaction

A highly enantio- and diastereoselective dynamic kinetic resolution (DKR) of configurationally labile 3-aryl indole-2-carbaldehydes is described. The DKR proceeds via a Rh-catalyzed intermolecular asymmetric reductive aldol reaction with acrylate esters, with simultaneous generation of three stereog...

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Autores: Rodríguez-Franco, Carlos, Ros, Abel, Merino, Pedro, Fernández, Rosario, Lassaletta, José M., Hornillos, Valentín
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2023
País:España
Institución:Consejo Superior de Investigaciones Científicas (CSIC)
Repositorio:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/346704
Acceso en línea:http://hdl.handle.net/10261/346704
Access Level:acceso abierto
Palabra clave:Asymmetric catalysis
Axial chirality
3-aryl indoles
Dynamic kinetic resolution
Rhodium
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spelling Dynamic Kinetic Resolution of Indole-Based Sulfenylated Heterobiaryls by Rhodium-Catalyzed Atroposelective Reductive Aldol ReactionRodríguez-Franco, CarlosRos, AbelMerino, PedroFernández, RosarioLassaletta, José M.Hornillos, ValentínAsymmetric catalysisAxial chirality3-aryl indolesDynamic kinetic resolutionRhodiumA highly enantio- and diastereoselective dynamic kinetic resolution (DKR) of configurationally labile 3-aryl indole-2-carbaldehydes is described. The DKR proceeds via a Rh-catalyzed intermolecular asymmetric reductive aldol reaction with acrylate esters, with simultaneous generation of three stereogenic elements. The strategy relies on the labilization of the stereogenic axis that takes place thanks to a transient Lewis acid–base interaction (LABI) between the formyl group and a thioether moiety strategically located at the ortho′ position. The atropisomeric indole products present a high degree of functionalization and can be further converted to a series of axially chiral derivatives, thereby expanding their potential application in drug discovery and asymmetric catalysis.We thank the Spanish Ministerio de Ciencia e Innovación (Grants PID2019-106358GB-C21, PID2019-106358GB-C22, PID2019-104090RB-100, contracts RYC-2017-22294 for V. H. and fellowship FPU18/02677 for C.R.-F.), European funding (ERDF), and Junta de Andalucía (Grants P18-FR-3531, P18- FR-644, US-1262867, and US-1260906) and the Regional Government of Aragón (Grupos 17R-34). The authors thank the resources from the supercomputers “Memento” and “Cierzo” and technical expertise and assistance provided by BIFI-ZCAM (Universidad de Zaragoza, Spain).Peer reviewedAmerican Chemical SocietyMinisterio de Ciencia e Innovación (España)Ministerio de Ciencia, Innovación y Universidades (España)Agencia Estatal de Investigación (España)Ministerio de Educación, Cultura y Deporte (España)European CommissionJunta de AndalucíaGobierno de AragónConsejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]202420242023info:eu-repo/semantics/articlehttp://purl.org/coar/resource_type/c_6501Publisher's versioninfo:eu-repo/semantics/publishedVersionapplication/pdfhttp://hdl.handle.net/10261/346704reponame: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 2017-2020/PID2019-106358GB-C21info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PID2019-106358GB-C22info:eu-repo/grantAgreement/AEI//RYC-2017-22294https://doi.org/10.1021/acscatal.3c03422Síinfo:eu-repo/semantics/openAccessoai:digital.csic.es:10261/3467042026-05-22T06:33:51Z
dc.title.none.fl_str_mv Dynamic Kinetic Resolution of Indole-Based Sulfenylated Heterobiaryls by Rhodium-Catalyzed Atroposelective Reductive Aldol Reaction
title Dynamic Kinetic Resolution of Indole-Based Sulfenylated Heterobiaryls by Rhodium-Catalyzed Atroposelective Reductive Aldol Reaction
spellingShingle Dynamic Kinetic Resolution of Indole-Based Sulfenylated Heterobiaryls by Rhodium-Catalyzed Atroposelective Reductive Aldol Reaction
Rodríguez-Franco, Carlos
Asymmetric catalysis
Axial chirality
3-aryl indoles
Dynamic kinetic resolution
Rhodium
title_short Dynamic Kinetic Resolution of Indole-Based Sulfenylated Heterobiaryls by Rhodium-Catalyzed Atroposelective Reductive Aldol Reaction
title_full Dynamic Kinetic Resolution of Indole-Based Sulfenylated Heterobiaryls by Rhodium-Catalyzed Atroposelective Reductive Aldol Reaction
title_fullStr Dynamic Kinetic Resolution of Indole-Based Sulfenylated Heterobiaryls by Rhodium-Catalyzed Atroposelective Reductive Aldol Reaction
title_full_unstemmed Dynamic Kinetic Resolution of Indole-Based Sulfenylated Heterobiaryls by Rhodium-Catalyzed Atroposelective Reductive Aldol Reaction
title_sort Dynamic Kinetic Resolution of Indole-Based Sulfenylated Heterobiaryls by Rhodium-Catalyzed Atroposelective Reductive Aldol Reaction
dc.creator.none.fl_str_mv Rodríguez-Franco, Carlos
Ros, Abel
Merino, Pedro
Fernández, Rosario
Lassaletta, José M.
Hornillos, Valentín
author Rodríguez-Franco, Carlos
author_facet Rodríguez-Franco, Carlos
Ros, Abel
Merino, Pedro
Fernández, Rosario
Lassaletta, José M.
Hornillos, Valentín
author_role author
author2 Ros, Abel
Merino, Pedro
Fernández, Rosario
Lassaletta, José M.
Hornillos, Valentín
author2_role author
author
author
author
author
dc.contributor.none.fl_str_mv Ministerio de Ciencia e Innovación (España)
Ministerio de Ciencia, Innovación y Universidades (España)
Agencia Estatal de Investigación (España)
Ministerio de Educación, Cultura y Deporte (España)
European Commission
Junta de Andalucía
Gobierno de Aragón
Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]
dc.subject.none.fl_str_mv Asymmetric catalysis
Axial chirality
3-aryl indoles
Dynamic kinetic resolution
Rhodium
topic Asymmetric catalysis
Axial chirality
3-aryl indoles
Dynamic kinetic resolution
Rhodium
description A highly enantio- and diastereoselective dynamic kinetic resolution (DKR) of configurationally labile 3-aryl indole-2-carbaldehydes is described. The DKR proceeds via a Rh-catalyzed intermolecular asymmetric reductive aldol reaction with acrylate esters, with simultaneous generation of three stereogenic elements. The strategy relies on the labilization of the stereogenic axis that takes place thanks to a transient Lewis acid–base interaction (LABI) between the formyl group and a thioether moiety strategically located at the ortho′ position. The atropisomeric indole products present a high degree of functionalization and can be further converted to a series of axially chiral derivatives, thereby expanding their potential application in drug discovery and asymmetric catalysis.
publishDate 2023
dc.date.none.fl_str_mv 2023
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/10261/346704
url http://hdl.handle.net/10261/346704
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 2017-2020/PID2019-106358GB-C21
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PID2019-106358GB-C22
info:eu-repo/grantAgreement/AEI//RYC-2017-22294
https://doi.org/10.1021/acscatal.3c03422
Sí
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv American Chemical Society
publisher.none.fl_str_mv American Chemical Society
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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