Understanding bond formation in polar one-step reactions. Topological analyses of the reaction between nitrones and lithium ynolates

The mechanism of the reaction between nitrones and lithium ynolates has been studied using DFT methods at M06-2X/cc-pVTZ/PCM=THF level. After the formation of a starting complex, without energy barrier, in which the lithium atom is coordinated to both nitrone and ynolate, the reaction takes place in...

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Detalles Bibliográficos
Autores: Roca-López, David, Polo, Víctor, Tejero, Tomás, Merino, Pedro
Tipo de recurso: artículo
Estado:Versión aceptada para publicación
Fecha de publicación:2015
País:España
Institución:Consejo Superior de Investigaciones Científicas (CSIC)
Repositorio:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/122613
Acceso en línea:http://hdl.handle.net/10261/122613
Access Level:acceso abierto
Palabra clave:Ynolates
Nitrones
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spelling Understanding bond formation in polar one-step reactions. Topological analyses of the reaction between nitrones and lithium ynolatesRoca-López, DavidPolo, VíctorTejero, TomásMerino, PedroYnolatesNitronesThe mechanism of the reaction between nitrones and lithium ynolates has been studied using DFT methods at M06-2X/cc-pVTZ/PCM=THF level. After the formation of a starting complex, without energy barrier, in which the lithium atom is coordinated to both nitrone and ynolate, the reaction takes place in one single kinetic step through an only transition structure. However, the formation of C-C- and C-O bonds takes place sequentially through a typical two-stage one-step process. A combined study of non-covalent interactions (NCI) and electron localization function (ELF) of selected points along the IRC of the reaction confirmed that, in the transition structure, only the C-C bond is being formed in some extent whereas an electrostatic interaction is present between carbon and oxygen atoms previous to the formation of the C-O bond. Indeed, the formation of the second C-O bond only begins when the first C-C bond is completely formed without formation of any intermediate. Once the C-C bond is formed and before the C-O bond formation starts the RMS gradient norm dips, approaching but not reaching zero giving rises to a hidden intermediate.This work was supported by the Ministerio de Economıá y Competitividad (MINECO) and FEDER Program (Madrid, Spain, project CTQ2013-44367-C2-1-P) and the Gobierno de Aragón (Zaragoza, Spain, Bioorganic Chemistry Group, E-10). D.R.-L. thanks the Spanish Ministry of Education (MEC) for a predoctoral grant (FPU program).Peer reviewedAmerican Chemical SocietyMinisterio de Economía y Competitividad (España)European CommissionGobierno de AragónMinisterio de Educación, Cultura y Deporte (España)Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]201520152015info:eu-repo/semantics/articlehttp://purl.org/coar/resource_type/c_6501Postprintinfo:eu-repo/semantics/acceptedVersionhttp://hdl.handle.net/10261/122613reponame:DIGITAL.CSIC. Repositorio Institucional del CSICinstname:Consejo Superior de Investigaciones Científicas (CSIC)Inglés#PLACEHOLDER_PARENT_METADATA_VALUE#info:eu-repo/grantAgreement/MINECO/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/CTQ2013-44367-C2-1-Phttp://dx.doi.org/10.1021/acs.joc.5b00413Síinfo:eu-repo/semantics/openAccessoai:digital.csic.es:10261/1226132026-05-22T06:33:51Z
dc.title.none.fl_str_mv Understanding bond formation in polar one-step reactions. Topological analyses of the reaction between nitrones and lithium ynolates
title Understanding bond formation in polar one-step reactions. Topological analyses of the reaction between nitrones and lithium ynolates
spellingShingle Understanding bond formation in polar one-step reactions. Topological analyses of the reaction between nitrones and lithium ynolates
Roca-López, David
Ynolates
Nitrones
title_short Understanding bond formation in polar one-step reactions. Topological analyses of the reaction between nitrones and lithium ynolates
title_full Understanding bond formation in polar one-step reactions. Topological analyses of the reaction between nitrones and lithium ynolates
title_fullStr Understanding bond formation in polar one-step reactions. Topological analyses of the reaction between nitrones and lithium ynolates
title_full_unstemmed Understanding bond formation in polar one-step reactions. Topological analyses of the reaction between nitrones and lithium ynolates
title_sort Understanding bond formation in polar one-step reactions. Topological analyses of the reaction between nitrones and lithium ynolates
dc.creator.none.fl_str_mv Roca-López, David
Polo, Víctor
Tejero, Tomás
Merino, Pedro
author Roca-López, David
author_facet Roca-López, David
Polo, Víctor
Tejero, Tomás
Merino, Pedro
author_role author
author2 Polo, Víctor
Tejero, Tomás
Merino, Pedro
author2_role author
author
author
dc.contributor.none.fl_str_mv Ministerio de Economía y Competitividad (España)
European Commission
Gobierno de Aragón
Ministerio de Educación, Cultura y Deporte (España)
Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]
dc.subject.none.fl_str_mv Ynolates
Nitrones
topic Ynolates
Nitrones
description The mechanism of the reaction between nitrones and lithium ynolates has been studied using DFT methods at M06-2X/cc-pVTZ/PCM=THF level. After the formation of a starting complex, without energy barrier, in which the lithium atom is coordinated to both nitrone and ynolate, the reaction takes place in one single kinetic step through an only transition structure. However, the formation of C-C- and C-O bonds takes place sequentially through a typical two-stage one-step process. A combined study of non-covalent interactions (NCI) and electron localization function (ELF) of selected points along the IRC of the reaction confirmed that, in the transition structure, only the C-C bond is being formed in some extent whereas an electrostatic interaction is present between carbon and oxygen atoms previous to the formation of the C-O bond. Indeed, the formation of the second C-O bond only begins when the first C-C bond is completely formed without formation of any intermediate. Once the C-C bond is formed and before the C-O bond formation starts the RMS gradient norm dips, approaching but not reaching zero giving rises to a hidden intermediate.
publishDate 2015
dc.date.none.fl_str_mv 2015
2015
2015
dc.type.none.fl_str_mv info:eu-repo/semantics/article
http://purl.org/coar/resource_type/c_6501
Postprint
info:eu-repo/semantics/acceptedVersion
format article
status_str acceptedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/10261/122613
url http://hdl.handle.net/10261/122613
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv #PLACEHOLDER_PARENT_METADATA_VALUE#
info:eu-repo/grantAgreement/MINECO/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/CTQ2013-44367-C2-1-P
http://dx.doi.org/10.1021/acs.joc.5b00413
Sí
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
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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