Electrophilic Hydrosilylation of Electron-Rich Alkenes Derived from Enamines

Chemicals and CAS Registry Numbers carbon 7440-44-0 platinum 7440-06-4 silicon 7440-21-3

Detalles Bibliográficos
Autores: Laglera-Gándara, Carlos J., Jiménez-Pérez, Julián, Fernández de Córdova, Francisco J., Ríos, Pablo, Conejero, Salvador
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:10261/375066
Acceso en línea:http://hdl.handle.net/10261/375066
https://api.elsevier.com/content/abstract/scopus_id/85194455781
Access Level:acceso abierto
Palabra clave:Enamine
Silylative dehydrocoupling
Platinum
Hydrosilylation
Outer-sphere mechanism
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spelling Electrophilic Hydrosilylation of Electron-Rich Alkenes Derived from EnaminesLaglera-Gándara, Carlos J.Jiménez-Pérez, JuliánFernández de Córdova, Francisco J.Ríos, PabloConejero, SalvadorEnamineSilylative dehydrocouplingPlatinumHydrosilylationOuter-sphere mechanismChemicals and CAS Registry Numbers carbon 7440-44-0 platinum 7440-06-4 silicon 7440-21-3The low-electron count, air-stable, platinum complexes [Pt(ItBu')(ItBu)][BArF] (C1) (ItBu=1,3-di-tert-butylimidazol-2-ylidene), [Pt(SiPh)3(ItBuiPr)2][BArF] (C2) (ItBuiPr=1-tert-butyl-3-iso-propylimidazol-2-ylidene), [Pt(SiPh)3(ItBuMe)2][BArF] (C3), [Pt(GePh3)(ItBuiPr)2][BArF] (C4), [Pt(GePh)3(ItBuMe)2][BArF] (C5) and [Pt(GeEt)3(ItBuMe)2][BArF] (C6) (ItBuMe=1-tert-butyl-3-methylimidazol-2-ylidene) are efficient catalysts (particularly the germyl derivatives) in both the silylative dehydrocoupling and hydrosilylation of electron rich alkenes derived from enamines. The steric hindrance exerted by the NHC ligand plays an important role in the selectivity of the reaction. Thus, bulky ligands are selective towards the silylative dehydrocoupling process whereas less sterically hindered promote the selective hydrosilylation reaction. The latter is, in addition, regioselective towards the β-carbon atom of both internal and terminal enamines, leading to β-aminosilanes. Moreover, the syn stereochemistry of the amino and silyl groups implies an anti Si-H bond addition across the double bond. All these facts point to a mechanistic picture that, according to experimental and computational studies, involves a non-classical hydrosilylation process through an outer-sphere mechanism in which a formal nucleophilic addition of the enamine to the silicon atom of a platinum σ-SiH complex is the key step. This is in sharp contrast with the classical Chalk-Harrod mechanism prevalent in platinum chemistry.This work was supported by the Spanish MCIN/AEI/10.13039/501100011033 (Grants PID2019\u2010109312GB\u2010I00, PID2022\u2010141925NB\u2010I00 and RED2022\u2010134287\u2010T), European FEDER funds and the Junta de Andaluc\u00EDa (project P20_00513). C.\u2005J. Laglera\u2010G\u00E1ndara thanks for a Margarita Salas grant financed by the European Union\u2010NextGenerationEU, Ministry of Universities and Recovery, Transformation and Resilience Plan, through a call from University of Oviedo (Grant MU\u201021\u2010UP2021\u2010030 53307942). The use of the computational facilities of the Supercomputing Center of Galicia (CESGA) is gratefully acknowledged.Peer reviewedWiley-LissMinisterio de Ciencia e Innovación (España)Ministerio de Ciencia, Innovación y Universidades (España)Universidad de OviedoJunta de AndalucíaCentro de Supercomputación de GaliciaLaglera-Gándara, Carlos J. [0000-0002-4480-1315]Jiménez-Pérez, Julián [0009-0006-0198-8104]Fernández de Córdova, Francisco J. [0000-0002-1784-2840]Ríos, Pablo [0000-0003-4467-4157]Conejero, Salvador [0000-0002-7278-8461]Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]202420242024info:eu-repo/semantics/articlehttp://purl.org/coar/resource_type/c_6501Publisher's versioninfo:eu-repo/semantics/publishedVersionaplication/pdfhttp://hdl.handle.net/10261/375066https://api.elsevier.com/content/abstract/scopus_id/85194455781reponame: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/PID2022-141925NB-I00info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PID2019-109312GB-I00Grant MU-21-UP2021-030 53307942https://doi.org/10.1002/anie.202404859Síinfo:eu-repo/semantics/openAccessoai:digital.csic.es:10261/3750662026-05-22T06:33:51Z
dc.title.none.fl_str_mv Electrophilic Hydrosilylation of Electron-Rich Alkenes Derived from Enamines
title Electrophilic Hydrosilylation of Electron-Rich Alkenes Derived from Enamines
spellingShingle Electrophilic Hydrosilylation of Electron-Rich Alkenes Derived from Enamines
Laglera-Gándara, Carlos J.
Enamine
Silylative dehydrocoupling
Platinum
Hydrosilylation
Outer-sphere mechanism
title_short Electrophilic Hydrosilylation of Electron-Rich Alkenes Derived from Enamines
title_full Electrophilic Hydrosilylation of Electron-Rich Alkenes Derived from Enamines
title_fullStr Electrophilic Hydrosilylation of Electron-Rich Alkenes Derived from Enamines
title_full_unstemmed Electrophilic Hydrosilylation of Electron-Rich Alkenes Derived from Enamines
title_sort Electrophilic Hydrosilylation of Electron-Rich Alkenes Derived from Enamines
dc.creator.none.fl_str_mv Laglera-Gándara, Carlos J.
Jiménez-Pérez, Julián
Fernández de Córdova, Francisco J.
Ríos, Pablo
Conejero, Salvador
author Laglera-Gándara, Carlos J.
author_facet Laglera-Gándara, Carlos J.
Jiménez-Pérez, Julián
Fernández de Córdova, Francisco J.
Ríos, Pablo
Conejero, Salvador
author_role author
author2 Jiménez-Pérez, Julián
Fernández de Córdova, Francisco J.
Ríos, Pablo
Conejero, Salvador
author2_role author
author
author
author
dc.contributor.none.fl_str_mv Ministerio de Ciencia e Innovación (España)
Ministerio de Ciencia, Innovación y Universidades (España)
Universidad de Oviedo
Junta de Andalucía
Centro de Supercomputación de Galicia
Laglera-Gándara, Carlos J. [0000-0002-4480-1315]
Jiménez-Pérez, Julián [0009-0006-0198-8104]
Fernández de Córdova, Francisco J. [0000-0002-1784-2840]
Ríos, Pablo [0000-0003-4467-4157]
Conejero, Salvador [0000-0002-7278-8461]
Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]
dc.subject.none.fl_str_mv Enamine
Silylative dehydrocoupling
Platinum
Hydrosilylation
Outer-sphere mechanism
topic Enamine
Silylative dehydrocoupling
Platinum
Hydrosilylation
Outer-sphere mechanism
description Chemicals and CAS Registry Numbers carbon 7440-44-0 platinum 7440-06-4 silicon 7440-21-3
publishDate 2024
dc.date.none.fl_str_mv 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/10261/375066
https://api.elsevier.com/content/abstract/scopus_id/85194455781
url http://hdl.handle.net/10261/375066
https://api.elsevier.com/content/abstract/scopus_id/85194455781
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#
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info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023/PID2022-141925NB-I00
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PID2019-109312GB-I00
Grant MU-21-UP2021-030 53307942
https://doi.org/10.1002/anie.202404859
Sí
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv aplication/pdf
dc.publisher.none.fl_str_mv Wiley-Liss
publisher.none.fl_str_mv Wiley-Liss
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
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