13C-Labeled Idohexopyranosyl Rings: Effects of Methyl Glycosidation and C6 Oxidation on Ring Conformational Equilibria
2017
Bose-Basu, Bidisha | Zhang, Wenhui | Kennedy, Jamie L. W. | Hadad, Matthew J. | Carmichael, Ian | Serianni, Anthony S.
An ensemble of JHH, JCH, and JCC values was measured in aqueous solutions of methyl α- and β-d-idohexopyranosides containing selective ¹³C-enrichment at various carbons. By comparing these J-couplings to those reported previously in the α- and β-d-idohexopyranoses, methyl glycosidation was found to affect ring conformational equilibria, with the percentages of ⁴C₁ forms based on ³JHH analysis as follows: α-d-idopyranose, ∼18%; methyl α-d-idopyranoside, ∼42%; methyl β-d-idopyranoside, ∼74%; β-d-idopyranose, 82%. JCH and JCC values were analyzed with assistance from theoretical values obtained from density functional theory (DFT) calculations. Linearized plots of the percentages of ⁴C₁ against limiting JCH and JCC values in the chair forms were used to (a) determine the compatibility of the experimental JCH and JCC values with ⁴C₁/¹C₄ ratios determined from JHH analysis and (b) determine the sensitivity of specific JCH and JCC values to ring conformation. Ring conformational equilibria for methyl idohexopyranosides differ significantly from those predicted from recent molecular dynamics (MD) simulations, indicating that equilibria determined by MD for ring configurations with energetically flat pseudorotational itineraries may not be quantitative. J-couplings in methyl α-l-[6-¹³C]idopyranosiduronic acid and methyl α-d-[6-¹³C]glucopyranosiduronic acid were measured as a function of solution pH. The ring conformational equilibrium is pH-dependent in the iduronic acid.
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