A joint experimental, in silico and NMR studies towards the rational design of iminium-based organocatalyst derived from renewable sources

Autores
Gerosa, Gabriela Guillermina; Spanevello, Rolando Angel; Suarez, Alejandra Graciela; Sarotti, Ariel Marcelo
Año de publicación
2015
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
An efficient organocatalyst for iminium-ionbased asymmetric Diels−Alder (DA) reactions has beenrationally designed. The most influential structure−activityrelationships were determined experimentally, while DFTcalculations and NMR studies provided further mechanisticinsight. This knowledge guided an in silico screening of 62different catalysts using an ONIOM(B3LYP/6-31G*:AM1)transition-state modeling, which showed good correlationbetween theory and experiment. The top-scored compoundwas easily synthesized from levoglucosenone, a biomass-derived chiral enone, and evaluated in the DA reaction between (E)-cinnamaldehyde and cyclopentadiene. In line with the computational finding, excellent results (up to 97% ee) were obtained. Inaddition, the catalyst could be easily recovered and reused with no loss in its catalytic activity.
Fil: Gerosa, Gabriela Guillermina. 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
Fil: Suarez, Alejandra Graciela. 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
Materia
Biomasa
Rmn
Organocatalizador
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:11336/6132
Acceder
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network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling A joint experimental, in silico and NMR studies towards the rational design of iminium-based organocatalyst derived from renewable sourcesGerosa, Gabriela GuillerminaSpanevello, Rolando AngelSuarez, Alejandra GracielaSarotti, Ariel MarceloBiomasaRmnOrganocatalizadorhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1An efficient organocatalyst for iminium-ionbased asymmetric Diels−Alder (DA) reactions has beenrationally designed. The most influential structure−activityrelationships were determined experimentally, while DFTcalculations and NMR studies provided further mechanisticinsight. This knowledge guided an in silico screening of 62different catalysts using an ONIOM(B3LYP/6-31G*:AM1)transition-state modeling, which showed good correlationbetween theory and experiment. The top-scored compoundwas easily synthesized from levoglucosenone, a biomass-derived chiral enone, and evaluated in the DA reaction between (E)-cinnamaldehyde and cyclopentadiene. In line with the computational finding, excellent results (up to 97% ee) were obtained. Inaddition, the catalyst could be easily recovered and reused with no loss in its catalytic activity.Fil: Gerosa, Gabriela Guillermina. 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; ArgentinaFil: Suarez, Alejandra Graciela. 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; ArgentinaAmerican Chemical Society2015-08info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/6132Gerosa, Gabriela Guillermina; Spanevello, Rolando Angel; Suarez, Alejandra Graciela; Sarotti, Ariel Marcelo; A joint experimental, in silico and NMR studies towards the rational design of iminium-based organocatalyst derived from renewable sources; American Chemical Society; Journal Of Organic Chemistry; 80; 15; 8-2015; 7626-76340022-3263enginfo:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/abs/10.1021/acs.joc.5b01214info:eu-repo/semantics/altIdentifier/doi/info:eu-repo/semantics/altIdentifier/doi/10.1021/acs.joc.5b01214info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T09:38:42Zoai:ri.conicet.gov.ar:11336/6132instacron: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 09:38:42.268CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv A joint experimental, in silico and NMR studies towards the rational design of iminium-based organocatalyst derived from renewable sources
title A joint experimental, in silico and NMR studies towards the rational design of iminium-based organocatalyst derived from renewable sources
spellingShingle A joint experimental, in silico and NMR studies towards the rational design of iminium-based organocatalyst derived from renewable sources
Gerosa, Gabriela Guillermina
Biomasa
Rmn
Organocatalizador
title_short A joint experimental, in silico and NMR studies towards the rational design of iminium-based organocatalyst derived from renewable sources
title_full A joint experimental, in silico and NMR studies towards the rational design of iminium-based organocatalyst derived from renewable sources
title_fullStr A joint experimental, in silico and NMR studies towards the rational design of iminium-based organocatalyst derived from renewable sources
title_full_unstemmed A joint experimental, in silico and NMR studies towards the rational design of iminium-based organocatalyst derived from renewable sources
title_sort A joint experimental, in silico and NMR studies towards the rational design of iminium-based organocatalyst derived from renewable sources
dc.creator.none.fl_str_mv Gerosa, Gabriela Guillermina
Spanevello, Rolando Angel
Suarez, Alejandra Graciela
Sarotti, Ariel Marcelo
author Gerosa, Gabriela Guillermina
author_facet Gerosa, Gabriela Guillermina
Spanevello, Rolando Angel
Suarez, Alejandra Graciela
Sarotti, Ariel Marcelo
author_role author
author2 Spanevello, Rolando Angel
Suarez, Alejandra Graciela
Sarotti, Ariel Marcelo
author2_role author
author
author
dc.subject.none.fl_str_mv Biomasa
Rmn
Organocatalizador
topic Biomasa
Rmn
Organocatalizador
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv An efficient organocatalyst for iminium-ionbased asymmetric Diels−Alder (DA) reactions has beenrationally designed. The most influential structure−activityrelationships were determined experimentally, while DFTcalculations and NMR studies provided further mechanisticinsight. This knowledge guided an in silico screening of 62different catalysts using an ONIOM(B3LYP/6-31G*:AM1)transition-state modeling, which showed good correlationbetween theory and experiment. The top-scored compoundwas easily synthesized from levoglucosenone, a biomass-derived chiral enone, and evaluated in the DA reaction between (E)-cinnamaldehyde and cyclopentadiene. In line with the computational finding, excellent results (up to 97% ee) were obtained. Inaddition, the catalyst could be easily recovered and reused with no loss in its catalytic activity.
Fil: Gerosa, Gabriela Guillermina. 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
Fil: Suarez, Alejandra Graciela. 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
description An efficient organocatalyst for iminium-ionbased asymmetric Diels−Alder (DA) reactions has beenrationally designed. The most influential structure−activityrelationships were determined experimentally, while DFTcalculations and NMR studies provided further mechanisticinsight. This knowledge guided an in silico screening of 62different catalysts using an ONIOM(B3LYP/6-31G*:AM1)transition-state modeling, which showed good correlationbetween theory and experiment. The top-scored compoundwas easily synthesized from levoglucosenone, a biomass-derived chiral enone, and evaluated in the DA reaction between (E)-cinnamaldehyde and cyclopentadiene. In line with the computational finding, excellent results (up to 97% ee) were obtained. Inaddition, the catalyst could be easily recovered and reused with no loss in its catalytic activity.
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/11336/6132
Gerosa, Gabriela Guillermina; Spanevello, Rolando Angel; Suarez, Alejandra Graciela; Sarotti, Ariel Marcelo; A joint experimental, in silico and NMR studies towards the rational design of iminium-based organocatalyst derived from renewable sources; American Chemical Society; Journal Of Organic Chemistry; 80; 15; 8-2015; 7626-7634
0022-3263
url http://hdl.handle.net/11336/6132
identifier_str_mv Gerosa, Gabriela Guillermina; Spanevello, Rolando Angel; Suarez, Alejandra Graciela; Sarotti, Ariel Marcelo; A joint experimental, in silico and NMR studies towards the rational design of iminium-based organocatalyst derived from renewable sources; American Chemical Society; Journal Of Organic Chemistry; 80; 15; 8-2015; 7626-7634
0022-3263
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/abs/10.1021/acs.joc.5b01214
info:eu-repo/semantics/altIdentifier/doi/
info:eu-repo/semantics/altIdentifier/doi/10.1021/acs.joc.5b01214
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
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
_version_ 1844613223595114496
score 13.070432

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