Experimental Evidence for Intramolecular Attractive Nonbonded C–F...H–C Interactions in 2′,3′-Dideoxy-4′-(fluoromethyl)nucleosides – Through-Space JCF and JHF NMR Coupling Constants, Correlation with Empirical Parameters of Solvent Polarity and Single-Crystal X-ray Structures

Vergani, Barbara; Viani, Fiorenza; Meille, Stefano V.; Farina, Alessandra; Bravo, Pierfrancesco

doi:10.1002/(sici)1099-0690(199901)1999:1<187::aid-ejoc187>3.3.co;2-i

Cited by 14 publications

(34 citation statements)

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“…5). The magnitude of the coupling is in agreement with previously reported through-space 1h J FH coupling constants, 22,23 considering that the 1 C 4 conformation is populated ∼20% of the time. Fig.…”

Section: Papersupporting

confidence: 91%

Exploration of conformational flexibility and hydrogen bonding of xylosides in different solvents, as a model system for enzyme active site interactions

et al. 2013

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The predominantly populated conformation of carbohydrates in solution does not necessarily represent the biologically active species; rather, any conformer accessible without too large an energy penalty may be present in a biological pathway. Thus, the conformational preferences of a naphthyl xyloside, which initiates in vivo synthesis of antiproliferative glycosaminoglycans, have been studied by using NMR spectroscopy in a variety of solvents. Equilibria comprising the conformations (4)C1, (2)SO and (1)C4 were found, with a strong dependence on the hydrogen bonding ability of the solvent. Studies of fluorinated analogues revealed a direct hydrogen bond from the hydroxyl group at C2 to the fluorine atom at C4 by a (1h)JF4,HO2 coupling. Hydrogen bond directionality was further established via comparisons of fluorinated levoglucosan molecules.

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Section: Papersupporting

confidence: 91%

Exploration of conformational flexibility and hydrogen bonding of xylosides in different solvents, as a model system for enzyme active site interactions

et al. 2013

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“…Splitting in Z 8 and Z 11 was not affected by solvent (CDCl 3 , toluene‐d 8 and CD 3 CN). Normally, coupling constants are not strongly solvent dependent, although Mele et al . reported a J FF solvent dependence for fluoronucleosides, which was related to hydrogen‐bonding ability of solvent.…”

Section: Resultsmentioning

confidence: 99%

Through‐space ¹⁹F–¹⁹F spin–spin coupling in ortho‐fluoro Z‐azobenzene

Rastogi

Rogers

Shi

et al. 2015

Magnetic Reson in Chemistry

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We report through-space (TS) (19)F-(19)F coupling for ortho-fluoro-substituted Z-azobenzenes. The magnitude of the TS-coupling constant ((TS) JFF ) ranged from 2.2-5.9 Hz. Using empirical formulas reported in the literature, these coupling constants correspond to non-bonded F-F distances (dFF) of 3.0-3.5 Å. These non-bonded distances are significantly smaller than those determined by X-ray crystallography or density functional theory, which argues that simple models of (19)F-(19)F TS spin-spin coupling solely based dFF are not applicable. (1)H, (13)C and (19)F data are reported for both the E and Z isomers of ten fluorinated azobenzenes. Density functional theory [B3YLP/6-311++G(d,p)] was used to calculate (19) F chemical shifts, and the calculated values deviated 0.3-10.0 ppm compared with experimental values.

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“…At higher water content, the interaction of water with other hydrogen atoms in the side chains increases and no preference is shown. The heteronuclear NOE experiments indicate the existence of tight ion pairs in the pure liquid, even in the presence of small amounts of water, and in DMSO solution [132].…”

Section: Nmr Spectroscopymentioning

confidence: 91%

Structural characteristics of alkylimidazolium-based salts containing fluoroanions

Matsumoto

Hagiwara

2007

Journal of Fluorine Chemistry

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An overview of recent structural studies on alkylimidazolium-based salts containing fluoroanions is presented. Alkylimidazolium cations have been most extensively used for syntheses of ionic liquids (room temperature molten salts) because they usually exhibit low melting points, low viscosities and high conductivities. This review mainly focuses on structures of alkylimidazolium-based salts combined with a fluorocomplex anion ((FH) n F À , BF 4 À , PF 6 À , AsF 6 À , SbF 6 À , NbF 6 À , TaF 6 À ), N(SO 2 CF 3 ) 2 À (TFSI À ) and OSO 2 CF 3 À . The first part describes crystal structures of these salts and the second part describes computational, spectroscopic and diffraction studies on their liquid structures. Related studies on ionic liquids of non-alkylimidazolium cation and non-fluoroanion are also briefly summarized. #

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Experimental Evidence for Intramolecular Attractive Nonbonded C–F...H–C Interactions in 2′,3′-Dideoxy-4′-(fluoromethyl)nucleosides – Through-Space JCF and JHF NMR Coupling Constants, Correlation with Empirical Parameters of Solvent Polarity and Single-Crystal X-ray Structures

Cited by 14 publications

References 5 publications

Exploration of conformational flexibility and hydrogen bonding of xylosides in different solvents, as a model system for enzyme active site interactions

Exploration of conformational flexibility and hydrogen bonding of xylosides in different solvents, as a model system for enzyme active site interactions

Through‐space ¹⁹F–¹⁹F spin–spin coupling in ortho‐fluoro Z‐azobenzene

Structural characteristics of alkylimidazolium-based salts containing fluoroanions

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Experimental Evidence for Intramolecular Attractive Nonbonded C–F...H–C Interactions in 2′,3′-Dideoxy-4′-(fluoromethyl)nucleosides – Through-Space JCF and JHF NMR Coupling Constants, Correlation with Empirical Parameters of Solvent Polarity and Single-Crystal X-ray Structures

Cited by 14 publications

References 5 publications

Exploration of conformational flexibility and hydrogen bonding of xylosides in different solvents, as a model system for enzyme active site interactions

Exploration of conformational flexibility and hydrogen bonding of xylosides in different solvents, as a model system for enzyme active site interactions

Through‐space 19F–19F spin–spin coupling in ortho‐fluoro Z‐azobenzene

Structural characteristics of alkylimidazolium-based salts containing fluoroanions

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Through‐space ¹⁹F–¹⁹F spin–spin coupling in ortho‐fluoro Z‐azobenzene