Prediction of anti and gauche vicinal proton‐proton coupling constants in carbohydrates: A simple additivity rule for pyranose rings
- 1 June 1980
- journal article
- research article
- Published by Wiley in Magnetic Resonance in Chemistry
- Vol. 13 (6) , 417-429
- https://doi.org/10.1002/mrc.1270130606
Abstract
The effect of the relative orientation and electronegativity of substituents on the magnitude of 3J(aa), 3J(ae) and 3J(ee) is well predicated by a simple set of additivity constants, valid for pyranose rings in carbohydrates. The proposed set of parameters is used to calculate 327 coupling constants [3J(HH)] in a variety of pyranosides and related compounds. A comparison with experimental values taken from the literature shows that couplings in molecules which are conformationally pure and underformed can be predicted with a surprising accuracy. An overall root‐mean‐square agreement of 0.29 Hz is attained for a selected group of 305 coupling values. A statistical breakdown of ΔJ(aa) and ΔJ(ae) [ΔJ=J(exp)‐J(calc)] along each carbon‐carbon bond in the pyranose systems reveals an unexpected degree of geometrical homogeneity.Keywords
This publication has 51 references indexed in Scilit:
- Application of ab initio molecular orbital calculations to the structural moieties of carbohydrates. 4Journal of the American Chemical Society, 1979
- Stereochemical Aspects of Proton Chemical Shifts. IX. Influence of O‐Alkyl Groups on the Chemical Shift of the Glycosidic Proton in Pyranoid SystemsBulletin des Sociétés Chimiques Belges, 1979
- Bausteine von Oligosacchariden, XI: Synthese α‐glycosidisch verknüpfter Disaccharide der 2‐Amino‐2‐desoxy‐D‐galactopyranoseEuropean Journal of Inorganic Chemistry, 1978
- 1H NMR Study of 2‐Deoxy‐D‐Arabino‐Hexopyranose (2‐Deoxy Glucopyranose), 2‐Deoxy‐D‐Lyxo‐Hexopyranose (2‐Deoxy Galactopyranose) and 2′‐Deoxy Lactose. Shift Increment Studies in 2‐Deoxy CarbohydratesBulletin des Sociétés Chimiques Belges, 1975
- The functional form of the karplus equationJournal of Magnetic Resonance (1969), 1972
- Molecular Orbital Calculations of Spin-Spin Coupling Constants for HydrocarbonsJournal of the American Chemical Society, 1966
- Vicinal Proton Coupling in Nuclear Magnetic ResonanceJournal of the American Chemical Society, 1963
- Substituent Effects on Nuclear Magnetic Resonance Coupling Constants and Chemical Shifts in a Saturated System: Hexachlorobicyclo [2.2.1]heptenesJournal of the American Chemical Society, 1963
- Fine Splittings in the Nuclear Magnetic Resonance Spectra of Alkyl DerivativesThe Journal of Chemical Physics, 1956
- Bond Energies and Polarities1Journal of the American Chemical Society, 1953