Iridium-catalyzed regio- and diastereoselective synthesis of C-substituted piperazines

Piperazine rings are essential motifs frequently found in commercial drugs. However, synthetic methodologies are mainly limited to N-substituted piperazines, preventing structural diversity. Disclosed herein is a straightforward catalytic method for the synthesis of complex C-substituted piperazines...

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Autores: Tarifa, Luis Miguel, Río, M. Pilar del, Asensio, Laura, López, José A., Ciriano, Miguel A., Geer, Ana M., Tejel, Cristina
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:10261/290330
Acceso en línea:http://hdl.handle.net/10261/290330
Access Level:acceso abierto
Palabra clave:Piperazines
Iridium
Homogeneous catalysis
[3 + 3]-cycloadditions
Imines
Trimethylamine N-oxide
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spelling Iridium-catalyzed regio- and diastereoselective synthesis of C-substituted piperazinesTarifa, Luis MiguelRío, M. Pilar delAsensio, LauraLópez, José A.Ciriano, Miguel A.Geer, Ana M.Tejel, CristinaPiperazinesIridiumHomogeneous catalysis[3 + 3]-cycloadditionsIminesTrimethylamine N-oxidePiperazine rings are essential motifs frequently found in commercial drugs. However, synthetic methodologies are mainly limited to N-substituted piperazines, preventing structural diversity. Disclosed herein is a straightforward catalytic method for the synthesis of complex C-substituted piperazines based on an uncommon head-to-head coupling of easily prepared imines. This 100% atom-economic process allows the selective formation of a sole diastereoisomer, a broad substrate scope, and a good functional group tolerance employing a bench-stable iridium catalyst under mild reaction conditions. Key to the success is the addition of N-oxides to the reaction mixture, as they notably enhance the catalytic activity and selectivity.The generous financial support from MCIN/AEI/10.13039/501100011033 (PID2020-119512GB-I00) and Gobierno de Aragón/FEDER, EU (GA/FEDER, Reactivity and Catalysis Inorganic Chemistry Group, E50_20D) is gratefully acknowledged. A.M.G. is thankful for Grant IJC2018-035231-I funded by MCIN/AEI/10.13039/501100011033, and L.T. thanks MICIIN/FEDER for an FPI fellowship.Peer reviewedAmerican Chemical SocietyMinisterio de Ciencia, Innovación y Universidades (España)European CommissionAgencia Estatal de Investigación (España)Gobierno de AragónConsejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]202320232023info:eu-repo/semantics/articlehttp://purl.org/coar/resource_type/c_6501Publisher's versioninfo:eu-repo/semantics/publishedVersionapplication/pdfhttp://hdl.handle.net/10261/290330reponame:DIGITAL.CSIC. Repositorio Institucional del CSICinstname:Consejo Superior de Investigaciones Científicas (CSIC)Inglés#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/PID2020-119512GB-I00info:eu-repo/grantAgreement/AEI//IJC2018-035231-IACS Catalysishttps://doi.org/10.1021/acscatal.2c05895Síinfo:eu-repo/semantics/openAccessoai:digital.csic.es:10261/2903302026-05-22T06:33:51Z
dc.title.none.fl_str_mv Iridium-catalyzed regio- and diastereoselective synthesis of C-substituted piperazines
title Iridium-catalyzed regio- and diastereoselective synthesis of C-substituted piperazines
spellingShingle Iridium-catalyzed regio- and diastereoselective synthesis of C-substituted piperazines
Tarifa, Luis Miguel
Piperazines
Iridium
Homogeneous catalysis
[3 + 3]-cycloadditions
Imines
Trimethylamine N-oxide
title_short Iridium-catalyzed regio- and diastereoselective synthesis of C-substituted piperazines
title_full Iridium-catalyzed regio- and diastereoselective synthesis of C-substituted piperazines
title_fullStr Iridium-catalyzed regio- and diastereoselective synthesis of C-substituted piperazines
title_full_unstemmed Iridium-catalyzed regio- and diastereoselective synthesis of C-substituted piperazines
title_sort Iridium-catalyzed regio- and diastereoselective synthesis of C-substituted piperazines
dc.creator.none.fl_str_mv Tarifa, Luis Miguel
Río, M. Pilar del
Asensio, Laura
López, José A.
Ciriano, Miguel A.
Geer, Ana M.
Tejel, Cristina
author Tarifa, Luis Miguel
author_facet Tarifa, Luis Miguel
Río, M. Pilar del
Asensio, Laura
López, José A.
Ciriano, Miguel A.
Geer, Ana M.
Tejel, Cristina
author_role author
author2 Río, M. Pilar del
Asensio, Laura
López, José A.
Ciriano, Miguel A.
Geer, Ana M.
Tejel, Cristina
author2_role author
author
author
author
author
author
dc.contributor.none.fl_str_mv Ministerio de Ciencia, Innovación y Universidades (España)
European Commission
Agencia Estatal de Investigación (España)
Gobierno de Aragón
Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]
dc.subject.none.fl_str_mv Piperazines
Iridium
Homogeneous catalysis
[3 + 3]-cycloadditions
Imines
Trimethylamine N-oxide
topic Piperazines
Iridium
Homogeneous catalysis
[3 + 3]-cycloadditions
Imines
Trimethylamine N-oxide
description Piperazine rings are essential motifs frequently found in commercial drugs. However, synthetic methodologies are mainly limited to N-substituted piperazines, preventing structural diversity. Disclosed herein is a straightforward catalytic method for the synthesis of complex C-substituted piperazines based on an uncommon head-to-head coupling of easily prepared imines. This 100% atom-economic process allows the selective formation of a sole diastereoisomer, a broad substrate scope, and a good functional group tolerance employing a bench-stable iridium catalyst under mild reaction conditions. Key to the success is the addition of N-oxides to the reaction mixture, as they notably enhance the catalytic activity and selectivity.
publishDate 2023
dc.date.none.fl_str_mv 2023
2023
2023
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/10261/290330
url http://hdl.handle.net/10261/290330
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#
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PID2020-119512GB-I00
info:eu-repo/grantAgreement/AEI//IJC2018-035231-I
ACS Catalysis
https://doi.org/10.1021/acscatal.2c05895
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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