Conformational Studies of Methyl 3-O-Methyl-α-d-arabinofuranoside: An Approach for Studying the Conformation of Furanose Rings
- 11 August 2001
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 123 (36), 8811-8824
- https://doi.org/10.1021/ja003768s
Abstract
A computational method for probing furanose conformation has been developed using a methylated monosaccharide derivative 1. First, a large library of conformers was generated by a systematic pseudo Monte Carlo search followed by optimization with the AMBER molecular mechanics force field. A subset of these conformers was then subjected to ab initio and density functional theory calculations in both the gas and aqueous phases. These calculations indicate that entropic contributions to the Gibbs free energy are important determinants of the Boltzmann distribution for the conformational preferences of 1 in the gas phase. The results obtained at each level of theory are discussed and compared with the experimentally determined conformer distribution from NMR studies in aqueous solution. In addition, the ability of each level of theory to reproduce the experimentally measured 1H-1H coupling constants in 1 is discussed. Empirical Karplus equations and density functional theory methods were used to determine average 3J(H1,H2), 3J(H2,H3), and 3J(H3,H4) for each level of theory. On the basis of this comparison, consideration of solvation with the MN-GSM model provided good agreement with the experimental data.Keywords
This publication has 100 references indexed in Scilit:
- Structures of Furanosides: A Study of the Conformational Space of Methyl α-d-Lyxofuranoside by Density Functional MethodsThe Journal of Physical Chemistry A, 2000
- A Computational Study of Methyl α-D-Arabinofuranoside: Effect of Ring Conformation on Structural Parameters and Energy ProfileJournal of the American Chemical Society, 1999
- An ab Initio Study of Fructose in the Gas PhaseThe Journal of Physical Chemistry A, 1999
- Calculation of NMR Chemical Shifts and Spin−Spin Coupling Constants in the Monosaccharide Methyl-β-d-xylopyranoside Using a Density Functional Theory ApproachThe Journal of Physical Chemistry A, 1997
- 13C−1H and 13C−13C Spin Couplings in [2‘-13C]2‘-Deoxyribonucleosides: Correlations with Molecular StructureJournal of the American Chemical Society, 1997
- Molecular architecture of araban, galactoglucan and welanCarbohydrate Polymers, 1994
- Molecular Modeling of Two Disaccharides Containing Fructopyranose Linked to GlucopyranoseJournal of Carbohydrate Chemistry, 1993
- Ribose puckering: structure, dynamics, energetics, and the pseudorotation cycleJournal of the American Chemical Society, 1986
- A full coupled-cluster singles and doubles model: The inclusion of disconnected triplesThe Journal of Chemical Physics, 1982
- Conformations of the Furanose Ring in Nucleic Acids and Other Carbohydrate Derivatives in the Solid State1Journal of the American Chemical Society, 1965