Chemical shifts and spin-spin coupling constants in Me alpha-D-xylopyranoside: A DFT approach

Chemical shieldings and coupling constants in a monosaccharide Me alpha -D- xylopyranoside were computed by density functional theory (DFT) method. The differences between the experimental and computed chemical shifts, for bot h DFT and MM3 geometries, showed that the method used reliably computes the se NMR parameters. The agreement with experimental values was also obtained for proton-proton and proton-carbon coupling constants across one or more bonds. Furthermore, the effect of conformation upon both NMR shielding tens ors (the values and orientation of its principal components) and couplings has also been investigated. The change of conformation around the C1-O1 lin kage resulted in variations of mainly anomeric proton and carbon chemical s hieldings as well as both the ring and O1 oxygens. The observed variations were found similar to those in Me beta -D-xylopyranoside [Hricovini, M.; Ma lkina, O. L.; Bizik, F; Turi Nagy, L.; Malkin, V. G. J. Phys. Chem. 1997, 1 01, 9756]. Similarly, the magnitudes of (1)J(C-H) and (3)J(C-H) varied upon the dihedral angle phi [H1-C1-O1-C-Me]. (1)J(C1-H1) couplings, based on DF T geometry, changed between 151.7 and 165.6 Hz with the smallest values fou nd for phi within -60 degrees to 60 degrees. (3)J(H1-C1-O1-CMe) varied betw een 0 and 11.2 Hz (DFT geometry) and showed the dependence comparable with the previous one for P anomer with one exception: the magnitude of (3)J(C-H ) for antiperiplanar conformation is about 3 Hz larger for the alpha anomer . Such differences could be important for the determination of glycosidic l inkage conformation of carbohydrates and may suggest that this type of depe ndence should be parametrized separately for alpha- and beta -linked carboh ydrates.