title: Conformational analysis of methyl 6-O-[(R)- and (S)-1-carboxyethyl]-alpha-D-galactopyranoside by MM and Langevin dynamics simulations.
abstract: The conformational space of methyl 6-O-[(R)- and (S)-1-carboxyethyl]-alpha-D-galactopyranoside has been investigated. A grid search employing energy minimization at each grid point over the three major degrees of freedom, namely phi, psi and omega, identified low energy regions. The R-isomer shows five low energy conformers within ca. 1 kcal mol(-1) of the global energy minimum. The S-isomer has two conformers within a few tenths of a kcal mol(-1) of the global energy minimum. Langevin dynamics simulations have been have been performed at 300 K for 30 ns of each isomer. The phi dihedral angle has as its major conformer (g-) for the R-isomer whereas it is the (g+) conformer for the S-isomer. For the psi dihedral angle the (t) conformer has the highest population for both isomers. The dihedral angle omega has the (g+) conformer most highly populated, both for the R- and S-isomer. The above five and two conformational states for the R- and S-isomers, respectively, make up 90% in each case of the populated states during the Langevin dynamics (LD) simulations. Rate constants for the omega dihedral angle have been calculated based on a number correlation function. Three bond homo- and heteronuclear, i.e. proton and carbon-13, coupling constants have been calculated from the dynamics trajectories for comparison to experimental values. The heteronuclear coupling constant H2',C6 has been measured for the S-isomer and found to be 3.3 Hz. The J value calculated from the LD simulations, namely 2.6 Hz, is in fair agreement with experiment. A comparison to the X-ray structure of the R-isomer shows that the conformation of the crystalline compound occupies the low energy region most highly populated as a single R-conformer (30%) during the LD simulations.
authors.affiliation: Department of Organic Chemistry, Arrhenius Laboratory Stockholm University, Sweden.
authors.forename: R
authors.initials: R
authors.lastname: Stenutz
authors.forename: G
authors.initials: G
authors.lastname: Widmalm
mesh_terms: D002236:Carbohydrate Conformation; D018360:Crystallography, X-Ray; D009682:Magnetic Resonance Spectroscopy; D008756:Methylgalactosides / Q000737:chemistry*; D008958:Models, Molecular; D011135:Polysaccharides, Bacterial / Q000737:chemistry; D013237:Stereoisomerism; D013816:Thermodynamics
chemical_list: D008756:Methylgalactosides; D011135:Polysaccharides, Bacterial; C111335:methyl 6-O-(1-carboxylethyl)galactopyranoside