Reactivity and Selectivity of Boron-Substituted Alkenes in the Diels-Alder Reaction with Cyclopentadiene. A Study of the Electron Charge Density and Its Laplacian

Autores
Vallejos, Margarita; Grimblat, Nicolas; Pellegrinet, Silvina Carla
Año de publicación
2014
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The effect of the nature of the boron moiety upon the reactivity and the selectivity of a variety of vinylboron dienophiles (1−12) in the Diels−Alder (DA) reaction was investigated using density functional theory and the quantum theory of atoms in molecules. The calculated reactivity of the dienophiles decreases in the order vinylborane (1) > dihalovinylboranes (2−4) > dialkylvinylboranes (5−7) ≈ vinyl boronic acid (8) > vinylboronates (9, 10) > vinyl MIDA boronate (11) ≈ vinyltrifluoroborate (12). The DA reactions of 1−7 were slightly endo-selective due to the stronger C6−B secondary orbital interaction in the endo transition structures (TSs) evaluated by the C6|B delocalization index. In the TSs of 5 and 7, a combination of electronic and steric factors reduce the endo selectivity. The moderate exo selectivity calculated for the DA reactions of boronates 8−11 was attributed mainly to the hydrogen bond between the oxygen atom of boronate moieties and one of the acidic hydrogens of the methylene of cyclopentadiene in the exo TSs, which also reduces the ability of the oxygen lone pairs to donate electron density into the vacant boron orbital. Interestingly, the cooperative effect between the two hydrogen bonds in the exo TS of the DA reaction of vinyltrifluoroborate (12) determines the almost exclusive exo selectivity predicted for this DA reaction. We propose that the relative reactivities of the dienophiles can be estimated by the charge density (ρr) and its Laplacian (∇2 ρr) at the (3,+1) critical point in the topology of ∇2 ρr, evaluated at the reactant molecules in the ground state. The profiles of the several topological parameters along the reaction are affected by the nature of the substituents attached to the boron atom and by the mode of addition (endo and exo) in the DA reactions.
Fil: Vallejos, Margarita. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Rosario. Instituto de Química Rosario; Argentina
Fil: Grimblat, Nicolas. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Rosario. Instituto de Química Rosario; Argentina
Fil: Pellegrinet, Silvina Carla. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Rosario. Instituto de Química Rosario; Argentina
Materia
Boron-Substituted Alkenes
Diels-Alder Reaction
Density Functional Theory
Quantum Theory of Atoms In Molecules
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:11336/6171

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oai_identifier_str oai:ri.conicet.gov.ar:11336/6171
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network_name_str CONICET Digital (CONICET)
spelling Reactivity and Selectivity of Boron-Substituted Alkenes in the Diels-Alder Reaction with Cyclopentadiene. A Study of the Electron Charge Density and Its LaplacianVallejos, MargaritaGrimblat, NicolasPellegrinet, Silvina CarlaBoron-Substituted AlkenesDiels-Alder ReactionDensity Functional TheoryQuantum Theory of Atoms In Moleculeshttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The effect of the nature of the boron moiety upon the reactivity and the selectivity of a variety of vinylboron dienophiles (1−12) in the Diels−Alder (DA) reaction was investigated using density functional theory and the quantum theory of atoms in molecules. The calculated reactivity of the dienophiles decreases in the order vinylborane (1) > dihalovinylboranes (2−4) > dialkylvinylboranes (5−7) ≈ vinyl boronic acid (8) > vinylboronates (9, 10) > vinyl MIDA boronate (11) ≈ vinyltrifluoroborate (12). The DA reactions of 1−7 were slightly endo-selective due to the stronger C6−B secondary orbital interaction in the endo transition structures (TSs) evaluated by the C6|B delocalization index. In the TSs of 5 and 7, a combination of electronic and steric factors reduce the endo selectivity. The moderate exo selectivity calculated for the DA reactions of boronates 8−11 was attributed mainly to the hydrogen bond between the oxygen atom of boronate moieties and one of the acidic hydrogens of the methylene of cyclopentadiene in the exo TSs, which also reduces the ability of the oxygen lone pairs to donate electron density into the vacant boron orbital. Interestingly, the cooperative effect between the two hydrogen bonds in the exo TS of the DA reaction of vinyltrifluoroborate (12) determines the almost exclusive exo selectivity predicted for this DA reaction. We propose that the relative reactivities of the dienophiles can be estimated by the charge density (ρr) and its Laplacian (∇2 ρr) at the (3,+1) critical point in the topology of ∇2 ρr, evaluated at the reactant molecules in the ground state. The profiles of the several topological parameters along the reaction are affected by the nature of the substituents attached to the boron atom and by the mode of addition (endo and exo) in the DA reactions.Fil: Vallejos, Margarita. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Rosario. Instituto de Química Rosario; ArgentinaFil: Grimblat, Nicolas. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Rosario. Instituto de Química Rosario; ArgentinaFil: Pellegrinet, Silvina Carla. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Rosario. Instituto de Química Rosario; ArgentinaAmerican Chemical Society2014-07info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/6171Vallejos, Margarita; Grimblat, Nicolas; Pellegrinet, Silvina Carla; Reactivity and Selectivity of Boron-Substituted Alkenes in the Diels-Alder Reaction with Cyclopentadiene. A Study of the Electron Charge Density and Its Laplacian; American Chemical Society; Journal of Physical Chemistry A; 118; 7-2014; 5559-55701089-5639enginfo:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/abs/10.1021/jp504972rinfo:eu-repo/semantics/altIdentifier/doi/10.1021/jp504972rinfo: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 Técnicas2025-09-29T09:44:43Zoai:ri.conicet.gov.ar:11336/6171instacron: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 09:44:43.932CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Reactivity and Selectivity of Boron-Substituted Alkenes in the Diels-Alder Reaction with Cyclopentadiene. A Study of the Electron Charge Density and Its Laplacian
title Reactivity and Selectivity of Boron-Substituted Alkenes in the Diels-Alder Reaction with Cyclopentadiene. A Study of the Electron Charge Density and Its Laplacian
spellingShingle Reactivity and Selectivity of Boron-Substituted Alkenes in the Diels-Alder Reaction with Cyclopentadiene. A Study of the Electron Charge Density and Its Laplacian
Vallejos, Margarita
Boron-Substituted Alkenes
Diels-Alder Reaction
Density Functional Theory
Quantum Theory of Atoms In Molecules
title_short Reactivity and Selectivity of Boron-Substituted Alkenes in the Diels-Alder Reaction with Cyclopentadiene. A Study of the Electron Charge Density and Its Laplacian
title_full Reactivity and Selectivity of Boron-Substituted Alkenes in the Diels-Alder Reaction with Cyclopentadiene. A Study of the Electron Charge Density and Its Laplacian
title_fullStr Reactivity and Selectivity of Boron-Substituted Alkenes in the Diels-Alder Reaction with Cyclopentadiene. A Study of the Electron Charge Density and Its Laplacian
title_full_unstemmed Reactivity and Selectivity of Boron-Substituted Alkenes in the Diels-Alder Reaction with Cyclopentadiene. A Study of the Electron Charge Density and Its Laplacian
title_sort Reactivity and Selectivity of Boron-Substituted Alkenes in the Diels-Alder Reaction with Cyclopentadiene. A Study of the Electron Charge Density and Its Laplacian
dc.creator.none.fl_str_mv Vallejos, Margarita
Grimblat, Nicolas
Pellegrinet, Silvina Carla
author Vallejos, Margarita
author_facet Vallejos, Margarita
Grimblat, Nicolas
Pellegrinet, Silvina Carla
author_role author
author2 Grimblat, Nicolas
Pellegrinet, Silvina Carla
author2_role author
author
dc.subject.none.fl_str_mv Boron-Substituted Alkenes
Diels-Alder Reaction
Density Functional Theory
Quantum Theory of Atoms In Molecules
topic Boron-Substituted Alkenes
Diels-Alder Reaction
Density Functional Theory
Quantum Theory of Atoms In Molecules
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 the nature of the boron moiety upon the reactivity and the selectivity of a variety of vinylboron dienophiles (1−12) in the Diels−Alder (DA) reaction was investigated using density functional theory and the quantum theory of atoms in molecules. The calculated reactivity of the dienophiles decreases in the order vinylborane (1) > dihalovinylboranes (2−4) > dialkylvinylboranes (5−7) ≈ vinyl boronic acid (8) > vinylboronates (9, 10) > vinyl MIDA boronate (11) ≈ vinyltrifluoroborate (12). The DA reactions of 1−7 were slightly endo-selective due to the stronger C6−B secondary orbital interaction in the endo transition structures (TSs) evaluated by the C6|B delocalization index. In the TSs of 5 and 7, a combination of electronic and steric factors reduce the endo selectivity. The moderate exo selectivity calculated for the DA reactions of boronates 8−11 was attributed mainly to the hydrogen bond between the oxygen atom of boronate moieties and one of the acidic hydrogens of the methylene of cyclopentadiene in the exo TSs, which also reduces the ability of the oxygen lone pairs to donate electron density into the vacant boron orbital. Interestingly, the cooperative effect between the two hydrogen bonds in the exo TS of the DA reaction of vinyltrifluoroborate (12) determines the almost exclusive exo selectivity predicted for this DA reaction. We propose that the relative reactivities of the dienophiles can be estimated by the charge density (ρr) and its Laplacian (∇2 ρr) at the (3,+1) critical point in the topology of ∇2 ρr, evaluated at the reactant molecules in the ground state. The profiles of the several topological parameters along the reaction are affected by the nature of the substituents attached to the boron atom and by the mode of addition (endo and exo) in the DA reactions.
Fil: Vallejos, Margarita. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Rosario. Instituto de Química Rosario; Argentina
Fil: Grimblat, Nicolas. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Rosario. Instituto de Química Rosario; Argentina
Fil: Pellegrinet, Silvina Carla. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Rosario. Instituto de Química Rosario; Argentina
description The effect of the nature of the boron moiety upon the reactivity and the selectivity of a variety of vinylboron dienophiles (1−12) in the Diels−Alder (DA) reaction was investigated using density functional theory and the quantum theory of atoms in molecules. The calculated reactivity of the dienophiles decreases in the order vinylborane (1) > dihalovinylboranes (2−4) > dialkylvinylboranes (5−7) ≈ vinyl boronic acid (8) > vinylboronates (9, 10) > vinyl MIDA boronate (11) ≈ vinyltrifluoroborate (12). The DA reactions of 1−7 were slightly endo-selective due to the stronger C6−B secondary orbital interaction in the endo transition structures (TSs) evaluated by the C6|B delocalization index. In the TSs of 5 and 7, a combination of electronic and steric factors reduce the endo selectivity. The moderate exo selectivity calculated for the DA reactions of boronates 8−11 was attributed mainly to the hydrogen bond between the oxygen atom of boronate moieties and one of the acidic hydrogens of the methylene of cyclopentadiene in the exo TSs, which also reduces the ability of the oxygen lone pairs to donate electron density into the vacant boron orbital. Interestingly, the cooperative effect between the two hydrogen bonds in the exo TS of the DA reaction of vinyltrifluoroborate (12) determines the almost exclusive exo selectivity predicted for this DA reaction. We propose that the relative reactivities of the dienophiles can be estimated by the charge density (ρr) and its Laplacian (∇2 ρr) at the (3,+1) critical point in the topology of ∇2 ρr, evaluated at the reactant molecules in the ground state. The profiles of the several topological parameters along the reaction are affected by the nature of the substituents attached to the boron atom and by the mode of addition (endo and exo) in the DA reactions.
publishDate 2014
dc.date.none.fl_str_mv 2014-07
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/11336/6171
Vallejos, Margarita; Grimblat, Nicolas; Pellegrinet, Silvina Carla; Reactivity and Selectivity of Boron-Substituted Alkenes in the Diels-Alder Reaction with Cyclopentadiene. A Study of the Electron Charge Density and Its Laplacian; American Chemical Society; Journal of Physical Chemistry A; 118; 7-2014; 5559-5570
1089-5639
url http://hdl.handle.net/11336/6171
identifier_str_mv Vallejos, Margarita; Grimblat, Nicolas; Pellegrinet, Silvina Carla; Reactivity and Selectivity of Boron-Substituted Alkenes in the Diels-Alder Reaction with Cyclopentadiene. A Study of the Electron Charge Density and Its Laplacian; American Chemical Society; Journal of Physical Chemistry A; 118; 7-2014; 5559-5570
1089-5639
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/jp504972r
info:eu-repo/semantics/altIdentifier/doi/10.1021/jp504972r
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
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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