DFT study on the molecular mechanism of the [4 + 2] cycloaddition between thiobenzophenone and arylalkenes via radical cations

Autores
Heredia, Luis Domingo; Pérez-Ruiz, Raul; Argüello, Juan Elias; Miranda, Hernán Miguel
Año de publicación
2009
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The mechanistic aspects of the radical cationic version of the [4 + 2] cycloaddition between thiobenzophenone 1 and three aryl-substituted alkenes 2a-c have been studied using DFT methods at the UB3LYP/6-31G level of theory. In the ground state, the Diels-Alder reaction follows an asynchronous concerted mechanism; the large activation energy associated with bond formation prevents this process. After generation of the radical cation (RC), formation of a molecular complex (MC) between 1 and 2a-c initiates a stepwise mechanism, with attack of the sulfur atom of 1 to the aryl-conjugated position of 2a-c. Subsequent ring closure is the rate-determining step of these cycloadditions. Methoxy or dimethylamino substitution at the aryl group, while stabilizing the corresponding RC, results in a less exothermic formation of MC and a significant increase of the cycloaddition barrier.
Fil: Heredia, Luis Domingo. Universidad de Valencia; España
Fil: Pérez-Ruiz, Raul. Universidad Politécnica de Valencia; España
Fil: Argüello, Juan Elias. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Fil: Miranda, Hernán Miguel. Universidad Politécnica de Valencia; España
Materia
Dft
Ion-Molecule Complex
Radical Cation
Reactivity
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/82615
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/82615
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling DFT study on the molecular mechanism of the [4 + 2] cycloaddition between thiobenzophenone and arylalkenes via radical cationsHeredia, Luis DomingoPérez-Ruiz, RaulArgüello, Juan EliasMiranda, Hernán MiguelDftIon-Molecule ComplexRadical CationReactivityhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The mechanistic aspects of the radical cationic version of the [4 + 2] cycloaddition between thiobenzophenone 1 and three aryl-substituted alkenes 2a-c have been studied using DFT methods at the UB3LYP/6-31G level of theory. In the ground state, the Diels-Alder reaction follows an asynchronous concerted mechanism; the large activation energy associated with bond formation prevents this process. After generation of the radical cation (RC), formation of a molecular complex (MC) between 1 and 2a-c initiates a stepwise mechanism, with attack of the sulfur atom of 1 to the aryl-conjugated position of 2a-c. Subsequent ring closure is the rate-determining step of these cycloadditions. Methoxy or dimethylamino substitution at the aryl group, while stabilizing the corresponding RC, results in a less exothermic formation of MC and a significant increase of the cycloaddition barrier.Fil: Heredia, Luis Domingo. Universidad de Valencia; EspañaFil: Pérez-Ruiz, Raul. Universidad Politécnica de Valencia; EspañaFil: Argüello, Juan Elias. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaFil: Miranda, Hernán Miguel. Universidad Politécnica de Valencia; EspañaAmerican Chemical Society2009-05info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/82615Heredia, Luis Domingo; Pérez-Ruiz, Raul; Argüello, Juan Elias; Miranda, Hernán Miguel; DFT study on the molecular mechanism of the [4 + 2] cycloaddition between thiobenzophenone and arylalkenes via radical cations; American Chemical Society; Journal of Physical Chemistry A; 113; 19; 5-2009; 5718-57221089-56391520-5215CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1021/jp900486einfo:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/jp900486einfo:eu-repo/semantics/altIdentifier/url/https://www.ncbi.nlm.nih.gov/pubmed/19385638info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T10:28:50Zoai:ri.conicet.gov.ar:11336/82615instacron:CONICETInstitucionalhttp://ri.conicet.gov.ar/Organismo científico-tecnológicoNo correspondehttp://ri.conicet.gov.ar/oai/requestdasensio@conicet.gov.ar; lcarlino@conicet.gov.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:34982025-09-29 10:28:50.36CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv DFT study on the molecular mechanism of the [4 + 2] cycloaddition between thiobenzophenone and arylalkenes via radical cations
title DFT study on the molecular mechanism of the [4 + 2] cycloaddition between thiobenzophenone and arylalkenes via radical cations
spellingShingle DFT study on the molecular mechanism of the [4 + 2] cycloaddition between thiobenzophenone and arylalkenes via radical cations
Heredia, Luis Domingo
Dft
Ion-Molecule Complex
Radical Cation
Reactivity
title_short DFT study on the molecular mechanism of the [4 + 2] cycloaddition between thiobenzophenone and arylalkenes via radical cations
title_full DFT study on the molecular mechanism of the [4 + 2] cycloaddition between thiobenzophenone and arylalkenes via radical cations
title_fullStr DFT study on the molecular mechanism of the [4 + 2] cycloaddition between thiobenzophenone and arylalkenes via radical cations
title_full_unstemmed DFT study on the molecular mechanism of the [4 + 2] cycloaddition between thiobenzophenone and arylalkenes via radical cations
title_sort DFT study on the molecular mechanism of the [4 + 2] cycloaddition between thiobenzophenone and arylalkenes via radical cations
dc.creator.none.fl_str_mv Heredia, Luis Domingo
Pérez-Ruiz, Raul
Argüello, Juan Elias
Miranda, Hernán Miguel
author Heredia, Luis Domingo
author_facet Heredia, Luis Domingo
Pérez-Ruiz, Raul
Argüello, Juan Elias
Miranda, Hernán Miguel
author_role author
author2 Pérez-Ruiz, Raul
Argüello, Juan Elias
Miranda, Hernán Miguel
author2_role author
author
author
dc.subject.none.fl_str_mv Dft
Ion-Molecule Complex
Radical Cation
Reactivity
topic Dft
Ion-Molecule Complex
Radical Cation
Reactivity
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv The mechanistic aspects of the radical cationic version of the [4 + 2] cycloaddition between thiobenzophenone 1 and three aryl-substituted alkenes 2a-c have been studied using DFT methods at the UB3LYP/6-31G level of theory. In the ground state, the Diels-Alder reaction follows an asynchronous concerted mechanism; the large activation energy associated with bond formation prevents this process. After generation of the radical cation (RC), formation of a molecular complex (MC) between 1 and 2a-c initiates a stepwise mechanism, with attack of the sulfur atom of 1 to the aryl-conjugated position of 2a-c. Subsequent ring closure is the rate-determining step of these cycloadditions. Methoxy or dimethylamino substitution at the aryl group, while stabilizing the corresponding RC, results in a less exothermic formation of MC and a significant increase of the cycloaddition barrier.
Fil: Heredia, Luis Domingo. Universidad de Valencia; España
Fil: Pérez-Ruiz, Raul. Universidad Politécnica de Valencia; España
Fil: Argüello, Juan Elias. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Fil: Miranda, Hernán Miguel. Universidad Politécnica de Valencia; España
description The mechanistic aspects of the radical cationic version of the [4 + 2] cycloaddition between thiobenzophenone 1 and three aryl-substituted alkenes 2a-c have been studied using DFT methods at the UB3LYP/6-31G level of theory. In the ground state, the Diels-Alder reaction follows an asynchronous concerted mechanism; the large activation energy associated with bond formation prevents this process. After generation of the radical cation (RC), formation of a molecular complex (MC) between 1 and 2a-c initiates a stepwise mechanism, with attack of the sulfur atom of 1 to the aryl-conjugated position of 2a-c. Subsequent ring closure is the rate-determining step of these cycloadditions. Methoxy or dimethylamino substitution at the aryl group, while stabilizing the corresponding RC, results in a less exothermic formation of MC and a significant increase of the cycloaddition barrier.
publishDate 2009
dc.date.none.fl_str_mv 2009-05
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
http://purl.org/coar/resource_type/c_6501
info:ar-repo/semantics/articulo
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/11336/82615
Heredia, Luis Domingo; Pérez-Ruiz, Raul; Argüello, Juan Elias; Miranda, Hernán Miguel; DFT study on the molecular mechanism of the [4 + 2] cycloaddition between thiobenzophenone and arylalkenes via radical cations; American Chemical Society; Journal of Physical Chemistry A; 113; 19; 5-2009; 5718-5722
1089-5639
1520-5215
CONICET Digital
CONICET
url http://hdl.handle.net/11336/82615
identifier_str_mv Heredia, Luis Domingo; Pérez-Ruiz, Raul; Argüello, Juan Elias; Miranda, Hernán Miguel; DFT study on the molecular mechanism of the [4 + 2] cycloaddition between thiobenzophenone and arylalkenes via radical cations; American Chemical Society; Journal of Physical Chemistry A; 113; 19; 5-2009; 5718-5722
1089-5639
1520-5215
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1021/jp900486e
info:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/jp900486e
info:eu-repo/semantics/altIdentifier/url/https://www.ncbi.nlm.nih.gov/pubmed/19385638
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
dc.format.none.fl_str_mv application/pdf
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:CONICET Digital (CONICET)
instname:Consejo Nacional de Investigaciones Científicas y Técnicas
reponame_str CONICET Digital (CONICET)
collection CONICET Digital (CONICET)
instname_str Consejo Nacional de Investigaciones Científicas y Técnicas
repository.name.fl_str_mv CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicas
repository.mail.fl_str_mv dasensio@conicet.gov.ar; lcarlino@conicet.gov.ar
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score 13.070432

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