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231225s2022 xx |||||o 00| ||eng c |
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|a 10.1002/mrc.5248
|2 doi
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|a pubmed25n1118.xml
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|a (DE-627)NLM335580998
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|a (NLM)35023222
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|a DE-627
|b ger
|c DE-627
|e rakwb
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|a eng
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1 |
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|a Soares, João Vitor
|e verfasserin
|4 aut
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|a Stereoelectronic interactions
|b A booster for 4 JHF transmission
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|c 2022
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|a Text
|b txt
|2 rdacontent
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|a ƒaComputermedien
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|2 rdamedia
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|a ƒa Online-Ressource
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|2 rdacarrier
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|a Date Completed 12.04.2022
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|a Date Revised 22.04.2022
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|a published: Print-Electronic
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|a Citation Status MEDLINE
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|a © 2022 John Wiley & Sons, Ltd.
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|a Long-range proton-fluorine coupling constants (n JHF ) are helpful for the structure elucidation of fluorinated molecules. However, their magnitude and sign can change with the relative position of coupled nuclei and the presence of substituents. Here, trans-4-tert-butyl-2-fluorocyclohexanone was used as a model compound for the study of the transmission of 4 JHF . In this compound, the 4 JH6axF was measured to be +5.1 Hz, which is five times larger than the remaining 4 JHF in the same molecule (4 JH4F = +1.0 Hz and 4 JH6eqF = +1.0 Hz). Through a combination of experimental data, natural bond orbital (NBO) and natural J-coupling (NJC) analyses, we observed that stereoelectronic interactions involving the π system of the carbonyl group are involved in the transmission pathway for the 4 JH6axF . Interactions containing the π system as an electron acceptor (e.g., σC6H6ax → π*C═O and σCF → π*C═O ) increase the value of the 4 JH6axF , while the interaction of the π system as an electron donor (e.g., πC═O → σ*CF ) decreases it. Additionally, the carbonyl group was shown not to be part of the transmission pathway of the diequatorial 4 JH6eqF coupling in cis-4-tert-butyl-2-fluorocyclohexanone, revealing that there is a crucial symmetry requirement that must be fulfilled for the π system to influence the value of the 4 JHF in these systems
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|a Journal Article
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|a Research Support, Non-U.S. Gov't
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|a coupling constant
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|a fluorine
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|a stereoelectronic interaction
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|a transmission pathway
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|a Fluorine
|2 NLM
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|a 284SYP0193
|2 NLM
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| 700 |
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|a Dal Poggetto, Guilherme
|e verfasserin
|4 aut
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| 700 |
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|a Viesser, Renan V
|e verfasserin
|4 aut
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| 700 |
1 |
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|a Couto, Uenifer R
|e verfasserin
|4 aut
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| 700 |
1 |
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|a Tormena, Cláudio F
|e verfasserin
|4 aut
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| 773 |
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|i Enthalten in
|t Magnetic resonance in chemistry : MRC
|d 1985
|g 60(2022), 5 vom: 15. Mai, Seite 481-488
|w (DE-627)NLM098179667
|x 1097-458X
|7 nnas
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| 773 |
1 |
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|g volume:60
|g year:2022
|g number:5
|g day:15
|g month:05
|g pages:481-488
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|u http://dx.doi.org/10.1002/mrc.5248
|3 Volltext
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