Evaluation of the Alicyclic Gauche Effect in 2‐Fluorocyclohexanone Analogs: a Combined NMR and DFT Study
Autor(a) principal: | |
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Data de Publicação: | 2020 |
Outros Autores: | , , , |
Tipo de documento: | Artigo |
Idioma: | eng |
Título da fonte: | Repositório Institucional da UFLA |
Texto Completo: | http://repositorio.ufla.br/jspui/handle/1/43086 |
Resumo: | Herein, we have investigated the effect of an endocyclic group (forming the N–C–C–F fragment) on the conformational preferences of 2‐fluorocyclohexanone analogs. A combined approach of nuclear magnetic resonance and density functional theory calculations was employed to assess the conformational equilibrium in several media. In turn, natural bond orbital analysis and the conformational behavior of other 2‐halocyclohexanone analogs were used to get more insights about the intramolecular interactions governing the conformer stabilities. Our results reveal that any stabilization from interactions featured in the gauche effect is overcome by a short‐range interaction of the fluorine substituent with the carbonyl group. Consequently, the gauche effect in heterocyclic compounds is not as stabilizing as in their acyclic counterparts. Only the electrostatic gauche effect takes place even in polar solvents owing to an attraction between the axial fluorine and an endocyclic quaternary ammonium group. |
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Evaluation of the Alicyclic Gauche Effect in 2‐Fluorocyclohexanone Analogs: a Combined NMR and DFT StudyAxial–equatorial equilibriumConformation analysisFluorine gauche effectHeterocyclesStereoelectronic effectsEquilíbrio axial-equatorialAnálise conformacionalEfeito gauche do fluoretoCompostos HeterocíclicosEfeitos EstereoeletrônicosHerein, we have investigated the effect of an endocyclic group (forming the N–C–C–F fragment) on the conformational preferences of 2‐fluorocyclohexanone analogs. A combined approach of nuclear magnetic resonance and density functional theory calculations was employed to assess the conformational equilibrium in several media. In turn, natural bond orbital analysis and the conformational behavior of other 2‐halocyclohexanone analogs were used to get more insights about the intramolecular interactions governing the conformer stabilities. Our results reveal that any stabilization from interactions featured in the gauche effect is overcome by a short‐range interaction of the fluorine substituent with the carbonyl group. Consequently, the gauche effect in heterocyclic compounds is not as stabilizing as in their acyclic counterparts. Only the electrostatic gauche effect takes place even in polar solvents owing to an attraction between the axial fluorine and an endocyclic quaternary ammonium group.Wiley‐VCH Verlag GmbH & Co. KGaA.2020-09-15T19:55:41Z2020-09-15T19:55:41Z2020-02info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/articleapplication/pdfSILVA, D. R. et al. Evaluation of the Alicyclic Gauche Effect in 2‐Fluorocyclohexanone Analogs: a Combined NMR and DFT Study. European Journal of Organic Chemistry, [S. I.], v. 2020, n. 7, p. 884–890, Feb. 2020. DOI: 10.1002/ejoc.201901815.http://repositorio.ufla.br/jspui/handle/1/43086European Journal of Organic Chemistryreponame:Repositório Institucional da UFLAinstname:Universidade Federal de Lavras (UFLA)instacron:UFLAAttribution-NonCommercial 4.0 Internationalhttp://creativecommons.org/licenses/by-nc/4.0/info:eu-repo/semantics/openAccessSilva, Daniela RodriguesZeoly, Lucas AndréCormanich, Rodrigo AntonioGuerra, Célia FonsecaFreitas, Matheus Puggina deeng2020-09-15T19:56:35Zoai:localhost:1/43086Repositório InstitucionalPUBhttp://repositorio.ufla.br/oai/requestnivaldo@ufla.br || repositorio.biblioteca@ufla.bropendoar:2020-09-15T19:56:35Repositório Institucional da UFLA - Universidade Federal de Lavras (UFLA)false |
dc.title.none.fl_str_mv |
Evaluation of the Alicyclic Gauche Effect in 2‐Fluorocyclohexanone Analogs: a Combined NMR and DFT Study |
title |
Evaluation of the Alicyclic Gauche Effect in 2‐Fluorocyclohexanone Analogs: a Combined NMR and DFT Study |
spellingShingle |
Evaluation of the Alicyclic Gauche Effect in 2‐Fluorocyclohexanone Analogs: a Combined NMR and DFT Study Silva, Daniela Rodrigues Axial–equatorial equilibrium Conformation analysis Fluorine gauche effect Heterocycles Stereoelectronic effects Equilíbrio axial-equatorial Análise conformacional Efeito gauche do fluoreto Compostos Heterocíclicos Efeitos Estereoeletrônicos |
title_short |
Evaluation of the Alicyclic Gauche Effect in 2‐Fluorocyclohexanone Analogs: a Combined NMR and DFT Study |
title_full |
Evaluation of the Alicyclic Gauche Effect in 2‐Fluorocyclohexanone Analogs: a Combined NMR and DFT Study |
title_fullStr |
Evaluation of the Alicyclic Gauche Effect in 2‐Fluorocyclohexanone Analogs: a Combined NMR and DFT Study |
title_full_unstemmed |
Evaluation of the Alicyclic Gauche Effect in 2‐Fluorocyclohexanone Analogs: a Combined NMR and DFT Study |
title_sort |
Evaluation of the Alicyclic Gauche Effect in 2‐Fluorocyclohexanone Analogs: a Combined NMR and DFT Study |
author |
Silva, Daniela Rodrigues |
author_facet |
Silva, Daniela Rodrigues Zeoly, Lucas André Cormanich, Rodrigo Antonio Guerra, Célia Fonseca Freitas, Matheus Puggina de |
author_role |
author |
author2 |
Zeoly, Lucas André Cormanich, Rodrigo Antonio Guerra, Célia Fonseca Freitas, Matheus Puggina de |
author2_role |
author author author author |
dc.contributor.author.fl_str_mv |
Silva, Daniela Rodrigues Zeoly, Lucas André Cormanich, Rodrigo Antonio Guerra, Célia Fonseca Freitas, Matheus Puggina de |
dc.subject.por.fl_str_mv |
Axial–equatorial equilibrium Conformation analysis Fluorine gauche effect Heterocycles Stereoelectronic effects Equilíbrio axial-equatorial Análise conformacional Efeito gauche do fluoreto Compostos Heterocíclicos Efeitos Estereoeletrônicos |
topic |
Axial–equatorial equilibrium Conformation analysis Fluorine gauche effect Heterocycles Stereoelectronic effects Equilíbrio axial-equatorial Análise conformacional Efeito gauche do fluoreto Compostos Heterocíclicos Efeitos Estereoeletrônicos |
description |
Herein, we have investigated the effect of an endocyclic group (forming the N–C–C–F fragment) on the conformational preferences of 2‐fluorocyclohexanone analogs. A combined approach of nuclear magnetic resonance and density functional theory calculations was employed to assess the conformational equilibrium in several media. In turn, natural bond orbital analysis and the conformational behavior of other 2‐halocyclohexanone analogs were used to get more insights about the intramolecular interactions governing the conformer stabilities. Our results reveal that any stabilization from interactions featured in the gauche effect is overcome by a short‐range interaction of the fluorine substituent with the carbonyl group. Consequently, the gauche effect in heterocyclic compounds is not as stabilizing as in their acyclic counterparts. Only the electrostatic gauche effect takes place even in polar solvents owing to an attraction between the axial fluorine and an endocyclic quaternary ammonium group. |
publishDate |
2020 |
dc.date.none.fl_str_mv |
2020-09-15T19:55:41Z 2020-09-15T19:55:41Z 2020-02 |
dc.type.status.fl_str_mv |
info:eu-repo/semantics/publishedVersion |
dc.type.driver.fl_str_mv |
info:eu-repo/semantics/article |
format |
article |
status_str |
publishedVersion |
dc.identifier.uri.fl_str_mv |
SILVA, D. R. et al. Evaluation of the Alicyclic Gauche Effect in 2‐Fluorocyclohexanone Analogs: a Combined NMR and DFT Study. European Journal of Organic Chemistry, [S. I.], v. 2020, n. 7, p. 884–890, Feb. 2020. DOI: 10.1002/ejoc.201901815. http://repositorio.ufla.br/jspui/handle/1/43086 |
identifier_str_mv |
SILVA, D. R. et al. Evaluation of the Alicyclic Gauche Effect in 2‐Fluorocyclohexanone Analogs: a Combined NMR and DFT Study. European Journal of Organic Chemistry, [S. I.], v. 2020, n. 7, p. 884–890, Feb. 2020. DOI: 10.1002/ejoc.201901815. |
url |
http://repositorio.ufla.br/jspui/handle/1/43086 |
dc.language.iso.fl_str_mv |
eng |
language |
eng |
dc.rights.driver.fl_str_mv |
Attribution-NonCommercial 4.0 International http://creativecommons.org/licenses/by-nc/4.0/ info:eu-repo/semantics/openAccess |
rights_invalid_str_mv |
Attribution-NonCommercial 4.0 International http://creativecommons.org/licenses/by-nc/4.0/ |
eu_rights_str_mv |
openAccess |
dc.format.none.fl_str_mv |
application/pdf |
dc.publisher.none.fl_str_mv |
Wiley‐VCH Verlag GmbH & Co. KGaA. |
publisher.none.fl_str_mv |
Wiley‐VCH Verlag GmbH & Co. KGaA. |
dc.source.none.fl_str_mv |
European Journal of Organic Chemistry reponame:Repositório Institucional da UFLA instname:Universidade Federal de Lavras (UFLA) instacron:UFLA |
instname_str |
Universidade Federal de Lavras (UFLA) |
instacron_str |
UFLA |
institution |
UFLA |
reponame_str |
Repositório Institucional da UFLA |
collection |
Repositório Institucional da UFLA |
repository.name.fl_str_mv |
Repositório Institucional da UFLA - Universidade Federal de Lavras (UFLA) |
repository.mail.fl_str_mv |
nivaldo@ufla.br || repositorio.biblioteca@ufla.br |
_version_ |
1807835082486972416 |