Understanding reactivity and regioselectivity in Diels–Alder reactions of a sugar-derived dienophile bearing two competing EWGs. An experimental and computational study

Autores
Giri, German Francisco; Sarotti, Ariel Marcelo; Spanevello, Rolando Angel
Año de publicación
2015
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The effect of an extra EWG in the reactivity and regioselectivity in Diels?Alder reactions of β-cyanolevoglucosenone and 4 different dienes was studied by a joint computational and experimental study. Conceptual DFT analysis successfully predicted an important enhancement in the reactivity, and correctly anticipated the regioselectivity in the reactions with isoprene. However, this static treatment failed when dealing the regiochemical preference of the reactions involving a substituted anthracene as diene. MPW1K/6-31G* calculations correctly reproduced the experimental observations. Based on the collected data, we found that when dealing with dienes and dienophiles with no clear electronically ac-tivated position, the ease of pyramidalization of the interacting atoms dictates the regioselectivity of the DA reaction.
Fil: Giri, German Francisco. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Rosario. Instituto de Química Rosario; Argentina
Fil: Sarotti, Ariel Marcelo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Rosario. Instituto de Química Rosario; Argentina
Fil: Spanevello, Rolando Angel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Rosario. Instituto de Química Rosario; Argentina
Materia
Reactivity
Regioselectivity
Diels-Alder
4-Cyanolevoglucosenone
Dft
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc-nd/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/6006
Acceder
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network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Understanding reactivity and regioselectivity in Diels–Alder reactions of a sugar-derived dienophile bearing two competing EWGs. An experimental and computational studyGiri, German FranciscoSarotti, Ariel MarceloSpanevello, Rolando AngelReactivityRegioselectivityDiels-Alder4-CyanolevoglucosenoneDfthttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The effect of an extra EWG in the reactivity and regioselectivity in Diels?Alder reactions of β-cyanolevoglucosenone and 4 different dienes was studied by a joint computational and experimental study. Conceptual DFT analysis successfully predicted an important enhancement in the reactivity, and correctly anticipated the regioselectivity in the reactions with isoprene. However, this static treatment failed when dealing the regiochemical preference of the reactions involving a substituted anthracene as diene. MPW1K/6-31G* calculations correctly reproduced the experimental observations. Based on the collected data, we found that when dealing with dienes and dienophiles with no clear electronically ac-tivated position, the ease of pyramidalization of the interacting atoms dictates the regioselectivity of the DA reaction.Fil: Giri, German Francisco. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Rosario. Instituto de Química Rosario; ArgentinaFil: Sarotti, Ariel Marcelo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Rosario. Instituto de Química Rosario; ArgentinaFil: Spanevello, Rolando Angel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Rosario. Instituto de Química Rosario; ArgentinaElsevier2015-08info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/6006Giri, German Francisco; Sarotti, Ariel Marcelo; Spanevello, Rolando Angel; Understanding reactivity and regioselectivity in Diels–Alder reactions of a sugar-derived dienophile bearing two competing EWGs. An experimental and computational study; Elsevier; Carbohydrate Research; 415; 8-2015; 54-590008-6215enginfo:eu-repo/semantics/altIdentifier/url/http://www.sciencedirect.com/science/article/pii/S0008621515002219info:eu-repo/semantics/altIdentifier/doi/info:eu-repo/semantics/altIdentifier/doi/10.1016/j.carres.2015.07.017info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-nd/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-03T09:55:21Zoai:ri.conicet.gov.ar:11336/6006instacron: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:34982025-09-03 09:55:22.225CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Understanding reactivity and regioselectivity in Diels–Alder reactions of a sugar-derived dienophile bearing two competing EWGs. An experimental and computational study
title Understanding reactivity and regioselectivity in Diels–Alder reactions of a sugar-derived dienophile bearing two competing EWGs. An experimental and computational study
spellingShingle Understanding reactivity and regioselectivity in Diels–Alder reactions of a sugar-derived dienophile bearing two competing EWGs. An experimental and computational study
Giri, German Francisco
Reactivity
Regioselectivity
Diels-Alder
4-Cyanolevoglucosenone
Dft
title_short Understanding reactivity and regioselectivity in Diels–Alder reactions of a sugar-derived dienophile bearing two competing EWGs. An experimental and computational study
title_full Understanding reactivity and regioselectivity in Diels–Alder reactions of a sugar-derived dienophile bearing two competing EWGs. An experimental and computational study
title_fullStr Understanding reactivity and regioselectivity in Diels–Alder reactions of a sugar-derived dienophile bearing two competing EWGs. An experimental and computational study
title_full_unstemmed Understanding reactivity and regioselectivity in Diels–Alder reactions of a sugar-derived dienophile bearing two competing EWGs. An experimental and computational study
title_sort Understanding reactivity and regioselectivity in Diels–Alder reactions of a sugar-derived dienophile bearing two competing EWGs. An experimental and computational study
dc.creator.none.fl_str_mv Giri, German Francisco
Sarotti, Ariel Marcelo
Spanevello, Rolando Angel
author Giri, German Francisco
author_facet Giri, German Francisco
Sarotti, Ariel Marcelo
Spanevello, Rolando Angel
author_role author
author2 Sarotti, Ariel Marcelo
Spanevello, Rolando Angel
author2_role author
author
dc.subject.none.fl_str_mv Reactivity
Regioselectivity
Diels-Alder
4-Cyanolevoglucosenone
Dft
topic Reactivity
Regioselectivity
Diels-Alder
4-Cyanolevoglucosenone
Dft
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 effect of an extra EWG in the reactivity and regioselectivity in Diels?Alder reactions of β-cyanolevoglucosenone and 4 different dienes was studied by a joint computational and experimental study. Conceptual DFT analysis successfully predicted an important enhancement in the reactivity, and correctly anticipated the regioselectivity in the reactions with isoprene. However, this static treatment failed when dealing the regiochemical preference of the reactions involving a substituted anthracene as diene. MPW1K/6-31G* calculations correctly reproduced the experimental observations. Based on the collected data, we found that when dealing with dienes and dienophiles with no clear electronically ac-tivated position, the ease of pyramidalization of the interacting atoms dictates the regioselectivity of the DA reaction.
Fil: Giri, German Francisco. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Rosario. Instituto de Química Rosario; Argentina
Fil: Sarotti, Ariel Marcelo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Rosario. Instituto de Química Rosario; Argentina
Fil: Spanevello, Rolando Angel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Rosario. Instituto de Química Rosario; Argentina
description The effect of an extra EWG in the reactivity and regioselectivity in Diels?Alder reactions of β-cyanolevoglucosenone and 4 different dienes was studied by a joint computational and experimental study. Conceptual DFT analysis successfully predicted an important enhancement in the reactivity, and correctly anticipated the regioselectivity in the reactions with isoprene. However, this static treatment failed when dealing the regiochemical preference of the reactions involving a substituted anthracene as diene. MPW1K/6-31G* calculations correctly reproduced the experimental observations. Based on the collected data, we found that when dealing with dienes and dienophiles with no clear electronically ac-tivated position, the ease of pyramidalization of the interacting atoms dictates the regioselectivity of the DA reaction.
publishDate 2015
dc.date.none.fl_str_mv 2015-08
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/11336/6006
Giri, German Francisco; Sarotti, Ariel Marcelo; Spanevello, Rolando Angel; Understanding reactivity and regioselectivity in Diels–Alder reactions of a sugar-derived dienophile bearing two competing EWGs. An experimental and computational study; Elsevier; Carbohydrate Research; 415; 8-2015; 54-59
0008-6215
url http://hdl.handle.net/11336/6006
identifier_str_mv Giri, German Francisco; Sarotti, Ariel Marcelo; Spanevello, Rolando Angel; Understanding reactivity and regioselectivity in Diels–Alder reactions of a sugar-derived dienophile bearing two competing EWGs. An experimental and computational study; Elsevier; Carbohydrate Research; 415; 8-2015; 54-59
0008-6215
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/http://www.sciencedirect.com/science/article/pii/S0008621515002219
info:eu-repo/semantics/altIdentifier/doi/
info:eu-repo/semantics/altIdentifier/doi/10.1016/j.carres.2015.07.017
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc-nd/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc-nd/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 13.13397

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