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
- Institución
- Consejo Nacional de Investigaciones Científicas y Técnicas
- OAI Identificador
- oai:ri.conicet.gov.ar:11336/6171
Ver los metadatos del registro completo
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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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1844613407075991552 |
score |
13.070432 |