On the unusual 2JC2-Hf coupling dependence on syn/anti CHO conformation in 5-X-furan-2-carboxaldehydes
A remarkable difference for 2JC2-H f, coupling constant in syn and anti conformers of 5-X-furan-2-carboxaldehydes (X = CH3, Ph, NO2, Br) and a rationalization of this difference are reported. On the basis of the current knowledge of the Fermi-contact term transmission, a rather unusual dual-coupling...
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Acceso en línea: | https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_07491581_v46_n9_p846_Perez http://hdl.handle.net/20.500.12110/paper_07491581_v46_n9_p846_Perez |
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paper:paper_07491581_v46_n9_p846_Perez2023-06-08T15:45:37Z On the unusual 2JC2-Hf coupling dependence on syn/anti CHO conformation in 5-X-furan-2-carboxaldehydes Contreras, Rubén Horacio Fermi-contact transmission Furfural Geminal NMR couplings NBO Through space aldehyde furan derivative article chemical model chemistry conformation electron methodology nuclear magnetic resonance spectroscopy quantum theory standard stereoisomerism Aldehydes Electrons Furans Magnetic Resonance Spectroscopy Models, Chemical Molecular Conformation Quantum Theory Reference Standards Stereoisomerism A remarkable difference for 2JC2-H f, coupling constant in syn and anti conformers of 5-X-furan-2-carboxaldehydes (X = CH3, Ph, NO2, Br) and a rationalization of this difference are reported. On the basis of the current knowledge of the Fermi-contact term transmission, a rather unusual dual-coupling pathway in the syn conformer is presented. The additional coupling pathway resembles somewhat that of the JH-H in homoallylic couplings, which are transmitted by hyperconjugative interactions involving the πC=C electronic system. The homoallylic coupling pathway can be labeled as σ*C-H ←-πc=c → σ*C-H. In the present case, this additional coupling pathway, using an analogous notation, can be labeled as σ* c2-cc ← LP1(O 1)⋯ LP2(Oc) → σ* Cc-Hf (σ*C2 -C c) where O1 and Oc stand for the ring and carbonyl O atoms, respectively. This additional coupling pathway is not activated in the anti conformers since both oxygen lone pairs do not overlap. Copyright © 2008 John Wiley & Sons, Ltd. Fil:Contreras, R.H. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. 2008 https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_07491581_v46_n9_p846_Perez http://hdl.handle.net/20.500.12110/paper_07491581_v46_n9_p846_Perez |
institution |
Universidad de Buenos Aires |
institution_str |
I-28 |
repository_str |
R-134 |
collection |
Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) |
topic |
Fermi-contact transmission Furfural Geminal NMR couplings NBO Through space aldehyde furan derivative article chemical model chemistry conformation electron methodology nuclear magnetic resonance spectroscopy quantum theory standard stereoisomerism Aldehydes Electrons Furans Magnetic Resonance Spectroscopy Models, Chemical Molecular Conformation Quantum Theory Reference Standards Stereoisomerism |
spellingShingle |
Fermi-contact transmission Furfural Geminal NMR couplings NBO Through space aldehyde furan derivative article chemical model chemistry conformation electron methodology nuclear magnetic resonance spectroscopy quantum theory standard stereoisomerism Aldehydes Electrons Furans Magnetic Resonance Spectroscopy Models, Chemical Molecular Conformation Quantum Theory Reference Standards Stereoisomerism Contreras, Rubén Horacio On the unusual 2JC2-Hf coupling dependence on syn/anti CHO conformation in 5-X-furan-2-carboxaldehydes |
topic_facet |
Fermi-contact transmission Furfural Geminal NMR couplings NBO Through space aldehyde furan derivative article chemical model chemistry conformation electron methodology nuclear magnetic resonance spectroscopy quantum theory standard stereoisomerism Aldehydes Electrons Furans Magnetic Resonance Spectroscopy Models, Chemical Molecular Conformation Quantum Theory Reference Standards Stereoisomerism |
description |
A remarkable difference for 2JC2-H f, coupling constant in syn and anti conformers of 5-X-furan-2-carboxaldehydes (X = CH3, Ph, NO2, Br) and a rationalization of this difference are reported. On the basis of the current knowledge of the Fermi-contact term transmission, a rather unusual dual-coupling pathway in the syn conformer is presented. The additional coupling pathway resembles somewhat that of the JH-H in homoallylic couplings, which are transmitted by hyperconjugative interactions involving the πC=C electronic system. The homoallylic coupling pathway can be labeled as σ*C-H ←-πc=c → σ*C-H. In the present case, this additional coupling pathway, using an analogous notation, can be labeled as σ* c2-cc ← LP1(O 1)⋯ LP2(Oc) → σ* Cc-Hf (σ*C2 -C c) where O1 and Oc stand for the ring and carbonyl O atoms, respectively. This additional coupling pathway is not activated in the anti conformers since both oxygen lone pairs do not overlap. Copyright © 2008 John Wiley & Sons, Ltd. |
author |
Contreras, Rubén Horacio |
author_facet |
Contreras, Rubén Horacio |
author_sort |
Contreras, Rubén Horacio |
title |
On the unusual 2JC2-Hf coupling dependence on syn/anti CHO conformation in 5-X-furan-2-carboxaldehydes |
title_short |
On the unusual 2JC2-Hf coupling dependence on syn/anti CHO conformation in 5-X-furan-2-carboxaldehydes |
title_full |
On the unusual 2JC2-Hf coupling dependence on syn/anti CHO conformation in 5-X-furan-2-carboxaldehydes |
title_fullStr |
On the unusual 2JC2-Hf coupling dependence on syn/anti CHO conformation in 5-X-furan-2-carboxaldehydes |
title_full_unstemmed |
On the unusual 2JC2-Hf coupling dependence on syn/anti CHO conformation in 5-X-furan-2-carboxaldehydes |
title_sort |
on the unusual 2jc2-hf coupling dependence on syn/anti cho conformation in 5-x-furan-2-carboxaldehydes |
publishDate |
2008 |
url |
https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_07491581_v46_n9_p846_Perez http://hdl.handle.net/20.500.12110/paper_07491581_v46_n9_p846_Perez |
work_keys_str_mv |
AT contrerasrubenhoracio ontheunusual2jc2hfcouplingdependenceonsynantichoconformationin5xfuran2carboxaldehydes |
_version_ |
1768543615672385536 |