1,2,3-Triazolium-Derived Mesoionic Carbene Ligands Bearing Chiral Sulfur-Based Moieties: Synthesis, Catalytic Properties, and Their Role in Chirality Transfer

1,2,3-Triazole-derived mesoionic carbenes (MICs) having a chiral sulfur functional group at the C5 position are easily available through a CuAAC between chiral alkynyl sulfoxides and different azides. The MICs form complexes with several metals (Au, Ag, Ir, Rh, and Ru) that are enantiomerically pure...

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Detalles Bibliográficos
Autores: Sierra, Miguel A., Torre, María C. de la
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2019
País:España
Institución:Consejo Superior de Investigaciones Científicas (CSIC)
Repositorio:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:dnet:digitalcsic_::165341177b19b4eb6da087eba974c093
Acceso en línea:http://hdl.handle.net/10261/194263
Access Level:acceso abierto
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spelling 1,2,3-Triazolium-Derived Mesoionic Carbene Ligands Bearing Chiral Sulfur-Based Moieties: Synthesis, Catalytic Properties, and Their Role in Chirality TransferSierra, Miguel A.Torre, María C. de la1,2,3-Triazole-derived mesoionic carbenes (MICs) having a chiral sulfur functional group at the C5 position are easily available through a CuAAC between chiral alkynyl sulfoxides and different azides. The MICs form complexes with several metals (Au, Ag, Ir, Rh, and Ru) that are enantiomerically pure. Moreover, enantiomerically pure MIC sulfinilimines are obtained from the corresponding sulfoxide retaining the chirality. Through this article, the participation of sulfoxide moieties in different catalytic and chirality transfer processes, as well as in discovering mechanistically new processes will be shown. The role of the sulfur chiral moiety in catalytic cycloisomerization and cycloisomerization-dimerization processes using Au-MIC catalysts is dual. The sulfur functional group either stabilizes intermediates in the catalytic cycle, allowing for the reaction to occur or significantly increases the selectivity of the cyclization processes. 1,2,3-Triazole MICs having chiral sulfoxides at C5 are extremely efficient in preparing chiral at the metal complexes by C-H insertion processes. The chiral at the metal half-sandwich complexes, having the enantiopure sulfur chiral group unaltered, experiences different reactions with complete retention of the configuration. Finally, mechanistically new processes, like the desulfinilation of 1,2,3-triazolium salts in Ag-MIC complexes have been uncovered. These still-nascent classes of compounds will offer opportunities for the discovery of novel catalytic applications and to study new mechanistically sound processes.Support for this work under grants CTQ2016-77555-C2-1-R to M.A.S., CTQ2016-77555-C2-2-R to M.C.T., and CTQ2016-81797-REDC Programa Redes Consolider from the MICUIN (Spain) is gratefully acknowledged. M.A.S. thanks the Fundación Ramón Areces for a grant from the XVII Concurso Nacional de Ayudas a la Investigación en Ciencias de la Vida y de la Materia (CIVP18A3938). We thank Dr. María Frutos and Marta García Avello for their essential contributions to our work in chiral sulfur MICs.Peer ReviewedACS PublicationsConsejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]2019201920192019info:eu-repo/semantics/articlehttp://purl.org/coar/resource_type/c_6501Publisher's versioninfo:eu-repo/semantics/publishedVersionhttp://hdl.handle.net/10261/194263reponame: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/MINECO/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/CTQ2016-77555-C2-1-Rinfo:eu-repo/grantAgreement/MINECO/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/CTQ2016-77555-C2-2-Rinfo:eu-repo/grantAgreement/MINECO/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/CTQ2016-81797-REDChttp://dx.doi.org/10.1021/acsomega.9b01285Síinfo:eu-repo/semantics/openAccessoai:dnet:digitalcsic_::165341177b19b4eb6da087eba974c0932026-05-22T06:33:51Z
dc.title.none.fl_str_mv 1,2,3-Triazolium-Derived Mesoionic Carbene Ligands Bearing Chiral Sulfur-Based Moieties: Synthesis, Catalytic Properties, and Their Role in Chirality Transfer
title 1,2,3-Triazolium-Derived Mesoionic Carbene Ligands Bearing Chiral Sulfur-Based Moieties: Synthesis, Catalytic Properties, and Their Role in Chirality Transfer
spellingShingle 1,2,3-Triazolium-Derived Mesoionic Carbene Ligands Bearing Chiral Sulfur-Based Moieties: Synthesis, Catalytic Properties, and Their Role in Chirality Transfer
Sierra, Miguel A.
title_short 1,2,3-Triazolium-Derived Mesoionic Carbene Ligands Bearing Chiral Sulfur-Based Moieties: Synthesis, Catalytic Properties, and Their Role in Chirality Transfer
title_full 1,2,3-Triazolium-Derived Mesoionic Carbene Ligands Bearing Chiral Sulfur-Based Moieties: Synthesis, Catalytic Properties, and Their Role in Chirality Transfer
title_fullStr 1,2,3-Triazolium-Derived Mesoionic Carbene Ligands Bearing Chiral Sulfur-Based Moieties: Synthesis, Catalytic Properties, and Their Role in Chirality Transfer
title_full_unstemmed 1,2,3-Triazolium-Derived Mesoionic Carbene Ligands Bearing Chiral Sulfur-Based Moieties: Synthesis, Catalytic Properties, and Their Role in Chirality Transfer
title_sort 1,2,3-Triazolium-Derived Mesoionic Carbene Ligands Bearing Chiral Sulfur-Based Moieties: Synthesis, Catalytic Properties, and Their Role in Chirality Transfer
dc.creator.none.fl_str_mv Sierra, Miguel A.
Torre, María C. de la
author Sierra, Miguel A.
author_facet Sierra, Miguel A.
Torre, María C. de la
author_role author
author2 Torre, María C. de la
author2_role author
dc.contributor.none.fl_str_mv Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]
description 1,2,3-Triazole-derived mesoionic carbenes (MICs) having a chiral sulfur functional group at the C5 position are easily available through a CuAAC between chiral alkynyl sulfoxides and different azides. The MICs form complexes with several metals (Au, Ag, Ir, Rh, and Ru) that are enantiomerically pure. Moreover, enantiomerically pure MIC sulfinilimines are obtained from the corresponding sulfoxide retaining the chirality. Through this article, the participation of sulfoxide moieties in different catalytic and chirality transfer processes, as well as in discovering mechanistically new processes will be shown. The role of the sulfur chiral moiety in catalytic cycloisomerization and cycloisomerization-dimerization processes using Au-MIC catalysts is dual. The sulfur functional group either stabilizes intermediates in the catalytic cycle, allowing for the reaction to occur or significantly increases the selectivity of the cyclization processes. 1,2,3-Triazole MICs having chiral sulfoxides at C5 are extremely efficient in preparing chiral at the metal complexes by C-H insertion processes. The chiral at the metal half-sandwich complexes, having the enantiopure sulfur chiral group unaltered, experiences different reactions with complete retention of the configuration. Finally, mechanistically new processes, like the desulfinilation of 1,2,3-triazolium salts in Ag-MIC complexes have been uncovered. These still-nascent classes of compounds will offer opportunities for the discovery of novel catalytic applications and to study new mechanistically sound processes.
publishDate 2019
dc.date.none.fl_str_mv 2019
2019
2019
2019
dc.type.none.fl_str_mv info:eu-repo/semantics/article
http://purl.org/coar/resource_type/c_6501
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info:eu-repo/semantics/publishedVersion
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status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/10261/194263
url http://hdl.handle.net/10261/194263
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
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info:eu-repo/grantAgreement/MINECO/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/CTQ2016-77555-C2-2-R
info:eu-repo/grantAgreement/MINECO/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/CTQ2016-81797-REDC
http://dx.doi.org/10.1021/acsomega.9b01285
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)
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