A Hydrogen Bond Rationale for the Enantioselective beta-Alkenylboration of Enones Catalyzed by O-Monoacyltartaric Acids

Autores
Grimblat, Nicolas; Sugiura, Masaharu; Pellegrinet, Silvina Carla
Año de publicación
2014
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
DFT calculations suggest that O-monoacyl L-tartaric acids catalyze the asymmetric conjugate alkenylboration of enones through transition structures that are stabilized by hydrogen-bonding interactions. Formation of a fivemembered acyloxyborane is proposed. The hydrogen of the free carboxy group derived from the catalyst interacts with the carbonyl group of the cyclic acyloxyborane, stabilizing the transition structure and reducing the flexibility of the system. Additional stabilizing nonclassical CH···O hydrogen-bond interactions seem to determine the observed enantioselectivity.
Fil: Grimblat, Nicolas. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Rosario. Instituto de Química Rosario; Argentina
Fil: Sugiura, Masaharu. Kumamoto University. Graduate School of Pharmaceutical Sciences; Japón
Fil: Pellegrinet, Silvina Carla. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Rosario. Instituto de Química Rosario; Argentina
Materia
Asymmetric Conjugate Alkenylboration
Organocatalysis
Dft Calculations
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:11336/6071
Acceder
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repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling A Hydrogen Bond Rationale for the Enantioselective beta-Alkenylboration of Enones Catalyzed by O-Monoacyltartaric AcidsGrimblat, NicolasSugiura, MasaharuPellegrinet, Silvina CarlaAsymmetric Conjugate AlkenylborationOrganocatalysisDft Calculationshttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1DFT calculations suggest that O-monoacyl L-tartaric acids catalyze the asymmetric conjugate alkenylboration of enones through transition structures that are stabilized by hydrogen-bonding interactions. Formation of a fivemembered acyloxyborane is proposed. The hydrogen of the free carboxy group derived from the catalyst interacts with the carbonyl group of the cyclic acyloxyborane, stabilizing the transition structure and reducing the flexibility of the system. Additional stabilizing nonclassical CH···O hydrogen-bond interactions seem to determine the observed enantioselectivity.Fil: Grimblat, Nicolas. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Rosario. Instituto de Química Rosario; ArgentinaFil: Sugiura, Masaharu. Kumamoto University. Graduate School of Pharmaceutical Sciences; JapónFil: Pellegrinet, Silvina Carla. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Rosario. Instituto de Química Rosario; ArgentinaAmerican Chemical Society2014-06info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/6071Grimblat, Nicolas; Sugiura, Masaharu; Pellegrinet, Silvina Carla; A Hydrogen Bond Rationale for the Enantioselective beta-Alkenylboration of Enones Catalyzed by O-Monoacyltartaric Acids; American Chemical Society; Journal of Organic Chemistry; 79; 14; 6-2014; 6754-67580022-3263enginfo:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/abs/10.1021/jo5012398info:eu-repo/semantics/altIdentifier/doi/10.1021/jo5012398info:eu-repo/semantics/altIdentifier/doi/info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T10:02:39Zoai:ri.conicet.gov.ar:11336/6071instacron: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 10:02:39.321CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv A Hydrogen Bond Rationale for the Enantioselective beta-Alkenylboration of Enones Catalyzed by O-Monoacyltartaric Acids
title A Hydrogen Bond Rationale for the Enantioselective beta-Alkenylboration of Enones Catalyzed by O-Monoacyltartaric Acids
spellingShingle A Hydrogen Bond Rationale for the Enantioselective beta-Alkenylboration of Enones Catalyzed by O-Monoacyltartaric Acids
Grimblat, Nicolas
Asymmetric Conjugate Alkenylboration
Organocatalysis
Dft Calculations
title_short A Hydrogen Bond Rationale for the Enantioselective beta-Alkenylboration of Enones Catalyzed by O-Monoacyltartaric Acids
title_full A Hydrogen Bond Rationale for the Enantioselective beta-Alkenylboration of Enones Catalyzed by O-Monoacyltartaric Acids
title_fullStr A Hydrogen Bond Rationale for the Enantioselective beta-Alkenylboration of Enones Catalyzed by O-Monoacyltartaric Acids
title_full_unstemmed A Hydrogen Bond Rationale for the Enantioselective beta-Alkenylboration of Enones Catalyzed by O-Monoacyltartaric Acids
title_sort A Hydrogen Bond Rationale for the Enantioselective beta-Alkenylboration of Enones Catalyzed by O-Monoacyltartaric Acids
dc.creator.none.fl_str_mv Grimblat, Nicolas
Sugiura, Masaharu
Pellegrinet, Silvina Carla
author Grimblat, Nicolas
author_facet Grimblat, Nicolas
Sugiura, Masaharu
Pellegrinet, Silvina Carla
author_role author
author2 Sugiura, Masaharu
Pellegrinet, Silvina Carla
author2_role author
author
dc.subject.none.fl_str_mv Asymmetric Conjugate Alkenylboration
Organocatalysis
Dft Calculations
topic Asymmetric Conjugate Alkenylboration
Organocatalysis
Dft Calculations
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv DFT calculations suggest that O-monoacyl L-tartaric acids catalyze the asymmetric conjugate alkenylboration of enones through transition structures that are stabilized by hydrogen-bonding interactions. Formation of a fivemembered acyloxyborane is proposed. The hydrogen of the free carboxy group derived from the catalyst interacts with the carbonyl group of the cyclic acyloxyborane, stabilizing the transition structure and reducing the flexibility of the system. Additional stabilizing nonclassical CH···O hydrogen-bond interactions seem to determine the observed enantioselectivity.
Fil: Grimblat, Nicolas. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Rosario. Instituto de Química Rosario; Argentina
Fil: Sugiura, Masaharu. Kumamoto University. Graduate School of Pharmaceutical Sciences; Japón
Fil: Pellegrinet, Silvina Carla. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Rosario. Instituto de Química Rosario; Argentina
description DFT calculations suggest that O-monoacyl L-tartaric acids catalyze the asymmetric conjugate alkenylboration of enones through transition structures that are stabilized by hydrogen-bonding interactions. Formation of a fivemembered acyloxyborane is proposed. The hydrogen of the free carboxy group derived from the catalyst interacts with the carbonyl group of the cyclic acyloxyborane, stabilizing the transition structure and reducing the flexibility of the system. Additional stabilizing nonclassical CH···O hydrogen-bond interactions seem to determine the observed enantioselectivity.
publishDate 2014
dc.date.none.fl_str_mv 2014-06
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/11336/6071
Grimblat, Nicolas; Sugiura, Masaharu; Pellegrinet, Silvina Carla; A Hydrogen Bond Rationale for the Enantioselective beta-Alkenylboration of Enones Catalyzed by O-Monoacyltartaric Acids; American Chemical Society; Journal of Organic Chemistry; 79; 14; 6-2014; 6754-6758
0022-3263
url http://hdl.handle.net/11336/6071
identifier_str_mv Grimblat, Nicolas; Sugiura, Masaharu; Pellegrinet, Silvina Carla; A Hydrogen Bond Rationale for the Enantioselective beta-Alkenylboration of Enones Catalyzed by O-Monoacyltartaric Acids; American Chemical Society; Journal of Organic Chemistry; 79; 14; 6-2014; 6754-6758
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/jo5012398
info:eu-repo/semantics/altIdentifier/doi/10.1021/jo5012398
info:eu-repo/semantics/altIdentifier/doi/
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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