Looking at the big picture in activation strain model/energy decomposition analysis: The case of the: Ortho - Para regioselectivity rule in Diels-Alder reactions

Autores
Grimblat, Nicolas; Sarotti, Ariel Marcelo
Año de publicación
2020
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The regioselectivity of the Diels-Alder reaction is predicted by the ortho-para rule which has been explained from FMO theory. Using DFT calculations, the activation-strain model and energy decomposition analysis we studied the reaction of methyl acrylate with four unsymmetrical dienes. We found that if the analysis is carried out considering the TS structures, the selectivity would not be explained by the interaction energy as expected considering the FMO arguments. However, a thorough analysis along the reaction path revealed that the interaction energy is responsible for the regioselectivity. A deeper analysis with the EDA model showed that the decisive term that accounts for the HOMO-LUMO interactions favors the ortho and para paths, as predicted by FMO arguments.
Fil: Grimblat, Nicolas. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina
Fil: Sarotti, Ariel Marcelo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina
Materia
DFT
Diels-Alder
Regioselectivity
EDA
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/141061
Acceder
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network_name_str CONICET Digital (CONICET)
spelling Looking at the big picture in activation strain model/energy decomposition analysis: The case of the: Ortho - Para regioselectivity rule in Diels-Alder reactionsGrimblat, NicolasSarotti, Ariel MarceloDFTDiels-AlderRegioselectivityEDAhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The regioselectivity of the Diels-Alder reaction is predicted by the ortho-para rule which has been explained from FMO theory. Using DFT calculations, the activation-strain model and energy decomposition analysis we studied the reaction of methyl acrylate with four unsymmetrical dienes. We found that if the analysis is carried out considering the TS structures, the selectivity would not be explained by the interaction energy as expected considering the FMO arguments. However, a thorough analysis along the reaction path revealed that the interaction energy is responsible for the regioselectivity. A deeper analysis with the EDA model showed that the decisive term that accounts for the HOMO-LUMO interactions favors the ortho and para paths, as predicted by FMO arguments.Fil: Grimblat, Nicolas. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; ArgentinaFil: Sarotti, Ariel Marcelo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; ArgentinaRoyal Society of Chemistry2020-02info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/141061Grimblat, Nicolas; Sarotti, Ariel Marcelo; Looking at the big picture in activation strain model/energy decomposition analysis: The case of the: Ortho - Para regioselectivity rule in Diels-Alder reactions; Royal Society of Chemistry; Organic & Biomolecular Chemistry; 18; 6; 2-2020; 1104-11111477-0520CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://pubs.rsc.org/en/content/articlelanding/2020/ob/c9ob02671a/unauthinfo:eu-repo/semantics/altIdentifier/doi/10.1039/C9OB02671Ainfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-10T13:20:57Zoai:ri.conicet.gov.ar:11336/141061instacron: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:34982025-09-10 13:20:57.653CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Looking at the big picture in activation strain model/energy decomposition analysis: The case of the: Ortho - Para regioselectivity rule in Diels-Alder reactions
title Looking at the big picture in activation strain model/energy decomposition analysis: The case of the: Ortho - Para regioselectivity rule in Diels-Alder reactions
spellingShingle Looking at the big picture in activation strain model/energy decomposition analysis: The case of the: Ortho - Para regioselectivity rule in Diels-Alder reactions
Grimblat, Nicolas
DFT
Diels-Alder
Regioselectivity
EDA
title_short Looking at the big picture in activation strain model/energy decomposition analysis: The case of the: Ortho - Para regioselectivity rule in Diels-Alder reactions
title_full Looking at the big picture in activation strain model/energy decomposition analysis: The case of the: Ortho - Para regioselectivity rule in Diels-Alder reactions
title_fullStr Looking at the big picture in activation strain model/energy decomposition analysis: The case of the: Ortho - Para regioselectivity rule in Diels-Alder reactions
title_full_unstemmed Looking at the big picture in activation strain model/energy decomposition analysis: The case of the: Ortho - Para regioselectivity rule in Diels-Alder reactions
title_sort Looking at the big picture in activation strain model/energy decomposition analysis: The case of the: Ortho - Para regioselectivity rule in Diels-Alder reactions
dc.creator.none.fl_str_mv Grimblat, Nicolas
Sarotti, Ariel Marcelo
author Grimblat, Nicolas
author_facet Grimblat, Nicolas
Sarotti, Ariel Marcelo
author_role author
author2 Sarotti, Ariel Marcelo
author2_role author
dc.subject.none.fl_str_mv DFT
Diels-Alder
Regioselectivity
EDA
topic DFT
Diels-Alder
Regioselectivity
EDA
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 regioselectivity of the Diels-Alder reaction is predicted by the ortho-para rule which has been explained from FMO theory. Using DFT calculations, the activation-strain model and energy decomposition analysis we studied the reaction of methyl acrylate with four unsymmetrical dienes. We found that if the analysis is carried out considering the TS structures, the selectivity would not be explained by the interaction energy as expected considering the FMO arguments. However, a thorough analysis along the reaction path revealed that the interaction energy is responsible for the regioselectivity. A deeper analysis with the EDA model showed that the decisive term that accounts for the HOMO-LUMO interactions favors the ortho and para paths, as predicted by FMO arguments.
Fil: Grimblat, Nicolas. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina
Fil: Sarotti, Ariel Marcelo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina
description The regioselectivity of the Diels-Alder reaction is predicted by the ortho-para rule which has been explained from FMO theory. Using DFT calculations, the activation-strain model and energy decomposition analysis we studied the reaction of methyl acrylate with four unsymmetrical dienes. We found that if the analysis is carried out considering the TS structures, the selectivity would not be explained by the interaction energy as expected considering the FMO arguments. However, a thorough analysis along the reaction path revealed that the interaction energy is responsible for the regioselectivity. A deeper analysis with the EDA model showed that the decisive term that accounts for the HOMO-LUMO interactions favors the ortho and para paths, as predicted by FMO arguments.
publishDate 2020
dc.date.none.fl_str_mv 2020-02
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/11336/141061
Grimblat, Nicolas; Sarotti, Ariel Marcelo; Looking at the big picture in activation strain model/energy decomposition analysis: The case of the: Ortho - Para regioselectivity rule in Diels-Alder reactions; Royal Society of Chemistry; Organic & Biomolecular Chemistry; 18; 6; 2-2020; 1104-1111
1477-0520
CONICET Digital
CONICET
url http://hdl.handle.net/11336/141061
identifier_str_mv Grimblat, Nicolas; Sarotti, Ariel Marcelo; Looking at the big picture in activation strain model/energy decomposition analysis: The case of the: Ortho - Para regioselectivity rule in Diels-Alder reactions; Royal Society of Chemistry; Organic & Biomolecular Chemistry; 18; 6; 2-2020; 1104-1111
1477-0520
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/https://pubs.rsc.org/en/content/articlelanding/2020/ob/c9ob02671a/unauth
info:eu-repo/semantics/altIdentifier/doi/10.1039/C9OB02671A
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
application/pdf
application/pdf
dc.publisher.none.fl_str_mv Royal Society of Chemistry
publisher.none.fl_str_mv Royal Society of Chemistry
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 12.48226

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