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

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 deri...

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Authors: Grimblat, Nicolas, Sugiura, Masaharu, Pellegrinet, Silvina Carla
Format: article
Status:Published version
Publication Date:2014
Country:Argentina
Institution:Consejo Nacional de Investigaciones Científicas y Técnicas
Repository:CONICET Digital (CONICET)
Language:English
OAI Identifier:oai:ri.conicet.gov.ar:11336/6071
Online Access:http://hdl.handle.net/11336/6071
Access Level:Open access
Keyword:Asymmetric Conjugate Alkenylboration
Organocatalysis
Dft Calculations
https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
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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 Técnicas2024-05-08T13:55:38Zoai: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:34982024-05-08 13:55:39.053CONICET 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
https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
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
https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
topic Asymmetric Conjugate Alkenylboration
Organocatalysis
Dft Calculations
https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
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
instname_str Consejo Nacional de Investigaciones Científicas y Técnicas
reponame_str CONICET Digital (CONICET)
collection CONICET Digital (CONICET)
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_ 1799195541248147456
score 15,228081

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