Understanding the participation of 3-nitropyridine in polar Diels-Alder reactions. A DFT study

Autores
Ormachea, Carla; Mancini, Pedro Maximo Emilio; Kneeteman, Maria Nelida; Domingo, Luis R.
Año de publicación
2015
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The reactivity of 3-nitropyridine acting as an electrophilic dienophile in polar Diels-Alder (P-DA) reactions toward three different dienes of increased nucleophilicity has been theoretically studied using DFT methods at the MPWB1K/6-31G(d) level. It has been observed that this aromatic heterocyclic system suffers cycloaddition reactions yielding isoquinoline derivatives. The present DFT study establishes that while the P-DA reactions with isoprene and 1-methoxy-1,3-butadiene take place through a two-stage one-step mechanism, the use of the strong nucleophilic Danishefsky's diene changes the mechanism to a two-step one with formation of a zwitterionic intermediate. These P-DA reactions are completely regioselective allowing the formation of a unique substituted isoquinoline. Analysis of the DFT reactivity indices at the ground state of the reagents correctly explains the reactivity and regioselectivity for these P-DA reactions.
Fil: Ormachea, Carla. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe; Argentina. Universidad Nacional del Litoral. Facultad de Ingeniería Química. Departamento de Química Orgánica; Argentina
Fil: Mancini, Pedro Maximo Emilio. Universidad Nacional del Litoral. Facultad de Ingeniería Química. Departamento de Química Orgánica; Argentina
Fil: Kneeteman, Maria Nelida. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe; Argentina. Universidad Nacional del Litoral. Facultad de Ingeniería Química. Departamento de Química Orgánica; Argentina
Fil: Domingo, Luis R.. Universidad de Valencia; España
Materia
3-NITROPYRIDINE
DFT INDICES
MOLECULAR MECHANISMS
PARR FUNCTIONS
POLAR DIELS-ALDER
REGIOSELECTIVITY
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:11336/84957
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/84957
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Understanding the participation of 3-nitropyridine in polar Diels-Alder reactions. A DFT studyOrmachea, CarlaMancini, Pedro Maximo EmilioKneeteman, Maria NelidaDomingo, Luis R.3-NITROPYRIDINEDFT INDICESMOLECULAR MECHANISMSPARR FUNCTIONSPOLAR DIELS-ALDERREGIOSELECTIVITYhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The reactivity of 3-nitropyridine acting as an electrophilic dienophile in polar Diels-Alder (P-DA) reactions toward three different dienes of increased nucleophilicity has been theoretically studied using DFT methods at the MPWB1K/6-31G(d) level. It has been observed that this aromatic heterocyclic system suffers cycloaddition reactions yielding isoquinoline derivatives. The present DFT study establishes that while the P-DA reactions with isoprene and 1-methoxy-1,3-butadiene take place through a two-stage one-step mechanism, the use of the strong nucleophilic Danishefsky's diene changes the mechanism to a two-step one with formation of a zwitterionic intermediate. These P-DA reactions are completely regioselective allowing the formation of a unique substituted isoquinoline. Analysis of the DFT reactivity indices at the ground state of the reagents correctly explains the reactivity and regioselectivity for these P-DA reactions.Fil: Ormachea, Carla. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe; Argentina. Universidad Nacional del Litoral. Facultad de Ingeniería Química. Departamento de Química Orgánica; ArgentinaFil: Mancini, Pedro Maximo Emilio. Universidad Nacional del Litoral. Facultad de Ingeniería Química. Departamento de Química Orgánica; ArgentinaFil: Kneeteman, Maria Nelida. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe; Argentina. Universidad Nacional del Litoral. Facultad de Ingeniería Química. Departamento de Química Orgánica; ArgentinaFil: Domingo, Luis R.. Universidad de Valencia; EspañaElsevier2015-11info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/84957Ormachea, Carla; Mancini, Pedro Maximo Emilio; Kneeteman, Maria Nelida; Domingo, Luis R.; Understanding the participation of 3-nitropyridine in polar Diels-Alder reactions. A DFT study; Elsevier; Computational and Theoretical Chemistry; 1072; 11-2015; 37-422210-271XCONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1016/j.comptc.2015.08.024info:eu-repo/semantics/altIdentifier/url/https://www.sciencedirect.com/science/article/pii/S2210271X1500359Xinfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-10-15T15:12:25Zoai:ri.conicet.gov.ar:11336/84957instacron: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:34982025-10-15 15:12:26.187CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Understanding the participation of 3-nitropyridine in polar Diels-Alder reactions. A DFT study
title Understanding the participation of 3-nitropyridine in polar Diels-Alder reactions. A DFT study
spellingShingle Understanding the participation of 3-nitropyridine in polar Diels-Alder reactions. A DFT study
Ormachea, Carla
3-NITROPYRIDINE
DFT INDICES
MOLECULAR MECHANISMS
PARR FUNCTIONS
POLAR DIELS-ALDER
REGIOSELECTIVITY
title_short Understanding the participation of 3-nitropyridine in polar Diels-Alder reactions. A DFT study
title_full Understanding the participation of 3-nitropyridine in polar Diels-Alder reactions. A DFT study
title_fullStr Understanding the participation of 3-nitropyridine in polar Diels-Alder reactions. A DFT study
title_full_unstemmed Understanding the participation of 3-nitropyridine in polar Diels-Alder reactions. A DFT study
title_sort Understanding the participation of 3-nitropyridine in polar Diels-Alder reactions. A DFT study
dc.creator.none.fl_str_mv Ormachea, Carla
Mancini, Pedro Maximo Emilio
Kneeteman, Maria Nelida
Domingo, Luis R.
author Ormachea, Carla
author_facet Ormachea, Carla
Mancini, Pedro Maximo Emilio
Kneeteman, Maria Nelida
Domingo, Luis R.
author_role author
author2 Mancini, Pedro Maximo Emilio
Kneeteman, Maria Nelida
Domingo, Luis R.
author2_role author
author
author
dc.subject.none.fl_str_mv 3-NITROPYRIDINE
DFT INDICES
MOLECULAR MECHANISMS
PARR FUNCTIONS
POLAR DIELS-ALDER
REGIOSELECTIVITY
topic 3-NITROPYRIDINE
DFT INDICES
MOLECULAR MECHANISMS
PARR FUNCTIONS
POLAR DIELS-ALDER
REGIOSELECTIVITY
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 reactivity of 3-nitropyridine acting as an electrophilic dienophile in polar Diels-Alder (P-DA) reactions toward three different dienes of increased nucleophilicity has been theoretically studied using DFT methods at the MPWB1K/6-31G(d) level. It has been observed that this aromatic heterocyclic system suffers cycloaddition reactions yielding isoquinoline derivatives. The present DFT study establishes that while the P-DA reactions with isoprene and 1-methoxy-1,3-butadiene take place through a two-stage one-step mechanism, the use of the strong nucleophilic Danishefsky's diene changes the mechanism to a two-step one with formation of a zwitterionic intermediate. These P-DA reactions are completely regioselective allowing the formation of a unique substituted isoquinoline. Analysis of the DFT reactivity indices at the ground state of the reagents correctly explains the reactivity and regioselectivity for these P-DA reactions.
Fil: Ormachea, Carla. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe; Argentina. Universidad Nacional del Litoral. Facultad de Ingeniería Química. Departamento de Química Orgánica; Argentina
Fil: Mancini, Pedro Maximo Emilio. Universidad Nacional del Litoral. Facultad de Ingeniería Química. Departamento de Química Orgánica; Argentina
Fil: Kneeteman, Maria Nelida. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe; Argentina. Universidad Nacional del Litoral. Facultad de Ingeniería Química. Departamento de Química Orgánica; Argentina
Fil: Domingo, Luis R.. Universidad de Valencia; España
description The reactivity of 3-nitropyridine acting as an electrophilic dienophile in polar Diels-Alder (P-DA) reactions toward three different dienes of increased nucleophilicity has been theoretically studied using DFT methods at the MPWB1K/6-31G(d) level. It has been observed that this aromatic heterocyclic system suffers cycloaddition reactions yielding isoquinoline derivatives. The present DFT study establishes that while the P-DA reactions with isoprene and 1-methoxy-1,3-butadiene take place through a two-stage one-step mechanism, the use of the strong nucleophilic Danishefsky's diene changes the mechanism to a two-step one with formation of a zwitterionic intermediate. These P-DA reactions are completely regioselective allowing the formation of a unique substituted isoquinoline. Analysis of the DFT reactivity indices at the ground state of the reagents correctly explains the reactivity and regioselectivity for these P-DA reactions.
publishDate 2015
dc.date.none.fl_str_mv 2015-11
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/11336/84957
Ormachea, Carla; Mancini, Pedro Maximo Emilio; Kneeteman, Maria Nelida; Domingo, Luis R.; Understanding the participation of 3-nitropyridine in polar Diels-Alder reactions. A DFT study; Elsevier; Computational and Theoretical Chemistry; 1072; 11-2015; 37-42
2210-271X
CONICET Digital
CONICET
url http://hdl.handle.net/11336/84957
identifier_str_mv Ormachea, Carla; Mancini, Pedro Maximo Emilio; Kneeteman, Maria Nelida; Domingo, Luis R.; Understanding the participation of 3-nitropyridine in polar Diels-Alder reactions. A DFT study; Elsevier; Computational and Theoretical Chemistry; 1072; 11-2015; 37-42
2210-271X
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1016/j.comptc.2015.08.024
info:eu-repo/semantics/altIdentifier/url/https://www.sciencedirect.com/science/article/pii/S2210271X1500359X
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 Elsevier
publisher.none.fl_str_mv Elsevier
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 13.22299

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