The effect of carbonyl group in the asymmetry of3,4J CH coupling constants in norbornanones

Autores
Dos Santos, Francisco P.; Tormena, Claudio F.; Contreras, Ruben Horacio; Rittner, Roberto; Magalhães, Alvicler
Año de publicación
2008
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
A rationalization of the known difference between the 3,4J C4H1 and 3,4JC1H4 couplings transmitted mainly through the 7-bridge in norbomanone is presented in terms of the effects of hyperconjugative interactions involving the carbonyl group. Theoretical and experimental studies of 3,4JCH couplings were carried out in 3-endo- and 3-exo-X-2-norbornanone derivatives (X = Cl, Br) and in exo- and endo-2-noborneol compounds. Hyperconjugative interactions were studied with the natural bond orbital (NBO) method. Hyperconjugative interactions involving the carbonyl π*C2 = O and σ*C2=O antibonding orbitais produce a decrease of three-bond contribution to both 3,4JC4H1 and 3,4JC1H4 couplings. However, the latter antibonding orbital also undergoes a strong σC3-C4 → σC2=O interaction, which defines an additional coupling pathway for 3,4JC4H1 but not for 3,4JC1H4. This pathway is similar to that known for homoallylic couplings, the only difference being the nature of the intermediate antibonding orbital; i.e. for 3,4JC4H1 it is of σ*-type, while in homoallylic couplings it is of π*-type. Copyright © 2007 John Wiley & Sons, Ltd.
Fil: Dos Santos, Francisco P.. Universidade Estadual de Campinas; Brasil
Fil: Tormena, Claudio F.. Universidade Estadual de Campinas; Brasil
Fil: Contreras, Ruben Horacio. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Física de Buenos Aires. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Física de Buenos Aires; Argentina
Fil: Rittner, Roberto. Universidade Estadual de Campinas; Brasil
Fil: Magalhães, Alvicler. Universidade de Sao Paulo; Brasil
Materia
3,4jch
Carbonyl Group
Nmr
Norbornanones
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:11336/61993
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/61993
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling The effect of carbonyl group in the asymmetry of3,4J CH coupling constants in norbornanonesDos Santos, Francisco P.Tormena, Claudio F.Contreras, Ruben HoracioRittner, RobertoMagalhães, Alvicler3,4jchCarbonyl GroupNmrNorbornanoneshttps://purl.org/becyt/ford/1.3https://purl.org/becyt/ford/1A rationalization of the known difference between the 3,4J C4H1 and 3,4JC1H4 couplings transmitted mainly through the 7-bridge in norbomanone is presented in terms of the effects of hyperconjugative interactions involving the carbonyl group. Theoretical and experimental studies of 3,4JCH couplings were carried out in 3-endo- and 3-exo-X-2-norbornanone derivatives (X = Cl, Br) and in exo- and endo-2-noborneol compounds. Hyperconjugative interactions were studied with the natural bond orbital (NBO) method. Hyperconjugative interactions involving the carbonyl π*C2 = O and σ*C2=O antibonding orbitais produce a decrease of three-bond contribution to both 3,4JC4H1 and 3,4JC1H4 couplings. However, the latter antibonding orbital also undergoes a strong σC3-C4 → σC2=O interaction, which defines an additional coupling pathway for 3,4JC4H1 but not for 3,4JC1H4. This pathway is similar to that known for homoallylic couplings, the only difference being the nature of the intermediate antibonding orbital; i.e. for 3,4JC4H1 it is of σ*-type, while in homoallylic couplings it is of π*-type. Copyright © 2007 John Wiley & Sons, Ltd.Fil: Dos Santos, Francisco P.. Universidade Estadual de Campinas; BrasilFil: Tormena, Claudio F.. Universidade Estadual de Campinas; BrasilFil: Contreras, Ruben Horacio. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Física de Buenos Aires. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Física de Buenos Aires; ArgentinaFil: Rittner, Roberto. Universidade Estadual de Campinas; BrasilFil: Magalhães, Alvicler. Universidade de Sao Paulo; BrasilJohn Wiley & Sons Ltd2008-02info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/61993Dos Santos, Francisco P.; Tormena, Claudio F.; Contreras, Ruben Horacio; Rittner, Roberto; Magalhães, Alvicler; The effect of carbonyl group in the asymmetry of3,4J CH coupling constants in norbornanones; John Wiley & Sons Ltd; Magnetic Resonance in Chemistry; 46; 2; 2-2008; 107-1090749-1581CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1002/mrc.2154info:eu-repo/semantics/altIdentifier/url/https://onlinelibrary.wiley.com/doi/abs/10.1002/mrc.2154info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-10T13:15:47Zoai:ri.conicet.gov.ar:11336/61993instacron: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:34982025-09-10 13:15:47.989CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv The effect of carbonyl group in the asymmetry of3,4J CH coupling constants in norbornanones
title The effect of carbonyl group in the asymmetry of3,4J CH coupling constants in norbornanones
spellingShingle The effect of carbonyl group in the asymmetry of3,4J CH coupling constants in norbornanones
Dos Santos, Francisco P.
3,4jch
Carbonyl Group
Nmr
Norbornanones
title_short The effect of carbonyl group in the asymmetry of3,4J CH coupling constants in norbornanones
title_full The effect of carbonyl group in the asymmetry of3,4J CH coupling constants in norbornanones
title_fullStr The effect of carbonyl group in the asymmetry of3,4J CH coupling constants in norbornanones
title_full_unstemmed The effect of carbonyl group in the asymmetry of3,4J CH coupling constants in norbornanones
title_sort The effect of carbonyl group in the asymmetry of3,4J CH coupling constants in norbornanones
dc.creator.none.fl_str_mv Dos Santos, Francisco P.
Tormena, Claudio F.
Contreras, Ruben Horacio
Rittner, Roberto
Magalhães, Alvicler
author Dos Santos, Francisco P.
author_facet Dos Santos, Francisco P.
Tormena, Claudio F.
Contreras, Ruben Horacio
Rittner, Roberto
Magalhães, Alvicler
author_role author
author2 Tormena, Claudio F.
Contreras, Ruben Horacio
Rittner, Roberto
Magalhães, Alvicler
author2_role author
author
author
author
dc.subject.none.fl_str_mv 3,4jch
Carbonyl Group
Nmr
Norbornanones
topic 3,4jch
Carbonyl Group
Nmr
Norbornanones
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.3
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv A rationalization of the known difference between the 3,4J C4H1 and 3,4JC1H4 couplings transmitted mainly through the 7-bridge in norbomanone is presented in terms of the effects of hyperconjugative interactions involving the carbonyl group. Theoretical and experimental studies of 3,4JCH couplings were carried out in 3-endo- and 3-exo-X-2-norbornanone derivatives (X = Cl, Br) and in exo- and endo-2-noborneol compounds. Hyperconjugative interactions were studied with the natural bond orbital (NBO) method. Hyperconjugative interactions involving the carbonyl π*C2 = O and σ*C2=O antibonding orbitais produce a decrease of three-bond contribution to both 3,4JC4H1 and 3,4JC1H4 couplings. However, the latter antibonding orbital also undergoes a strong σC3-C4 → σC2=O interaction, which defines an additional coupling pathway for 3,4JC4H1 but not for 3,4JC1H4. This pathway is similar to that known for homoallylic couplings, the only difference being the nature of the intermediate antibonding orbital; i.e. for 3,4JC4H1 it is of σ*-type, while in homoallylic couplings it is of π*-type. Copyright © 2007 John Wiley & Sons, Ltd.
Fil: Dos Santos, Francisco P.. Universidade Estadual de Campinas; Brasil
Fil: Tormena, Claudio F.. Universidade Estadual de Campinas; Brasil
Fil: Contreras, Ruben Horacio. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Física de Buenos Aires. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Física de Buenos Aires; Argentina
Fil: Rittner, Roberto. Universidade Estadual de Campinas; Brasil
Fil: Magalhães, Alvicler. Universidade de Sao Paulo; Brasil
description A rationalization of the known difference between the 3,4J C4H1 and 3,4JC1H4 couplings transmitted mainly through the 7-bridge in norbomanone is presented in terms of the effects of hyperconjugative interactions involving the carbonyl group. Theoretical and experimental studies of 3,4JCH couplings were carried out in 3-endo- and 3-exo-X-2-norbornanone derivatives (X = Cl, Br) and in exo- and endo-2-noborneol compounds. Hyperconjugative interactions were studied with the natural bond orbital (NBO) method. Hyperconjugative interactions involving the carbonyl π*C2 = O and σ*C2=O antibonding orbitais produce a decrease of three-bond contribution to both 3,4JC4H1 and 3,4JC1H4 couplings. However, the latter antibonding orbital also undergoes a strong σC3-C4 → σC2=O interaction, which defines an additional coupling pathway for 3,4JC4H1 but not for 3,4JC1H4. This pathway is similar to that known for homoallylic couplings, the only difference being the nature of the intermediate antibonding orbital; i.e. for 3,4JC4H1 it is of σ*-type, while in homoallylic couplings it is of π*-type. Copyright © 2007 John Wiley & Sons, Ltd.
publishDate 2008
dc.date.none.fl_str_mv 2008-02
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/11336/61993
Dos Santos, Francisco P.; Tormena, Claudio F.; Contreras, Ruben Horacio; Rittner, Roberto; Magalhães, Alvicler; The effect of carbonyl group in the asymmetry of3,4J CH coupling constants in norbornanones; John Wiley & Sons Ltd; Magnetic Resonance in Chemistry; 46; 2; 2-2008; 107-109
0749-1581
CONICET Digital
CONICET
url http://hdl.handle.net/11336/61993
identifier_str_mv Dos Santos, Francisco P.; Tormena, Claudio F.; Contreras, Ruben Horacio; Rittner, Roberto; Magalhães, Alvicler; The effect of carbonyl group in the asymmetry of3,4J CH coupling constants in norbornanones; John Wiley & Sons Ltd; Magnetic Resonance in Chemistry; 46; 2; 2-2008; 107-109
0749-1581
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1002/mrc.2154
info:eu-repo/semantics/altIdentifier/url/https://onlinelibrary.wiley.com/doi/abs/10.1002/mrc.2154
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 John Wiley & Sons Ltd
publisher.none.fl_str_mv John Wiley & Sons Ltd
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 12.993085

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