13C-Labeled Idohexopyranosyl Rings: Effects of Methyl Glycosidation and C6 Oxidation on Ring Conformational Equilibria

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• 作者：Bidisha Bose-Basu ; Wenhui Zhang ; Jamie L. W. Kennedy ; Matthew J. Hadad ; Ian Carmichael ; Anthony S. Serianni
• 刊名：Journal of Organic Chemistry
• 出版年：2017
• 出版时间：February 3, 2017
• 年：2017
• 卷：82
• 期：3
• 页码：1356-1370
• 全文大小：909K
• ISSN：1520-6904

文摘

An ensemble of J<sub>HHsub>, J<sub>CHsub>, and J<sub>CCsub> values was measured in aqueous solutions of methyl α- and β-<span class="smallcaps">dspan>-idohexopyranosides containing selective <sup>13sup>C-enrichment at various carbons. By comparing these J-couplings to those reported previously in the α- and β-<span class="smallcaps">dspan>-idohexopyranoses, methyl glycosidation was found to affect ring conformational equilibria, with the percentages of <sup>4sup>C<sub>1sub> forms based on <sup>3sup>J<sub>HHsub> analysis as follows: α-<span class="smallcaps">dspan>-idopyranose, ∼18%; methyl α-<span class="smallcaps">dspan>-idopyranoside, ∼42%; methyl β-<span class="smallcaps">dspan>-idopyranoside, ∼74%; β-<span class="smallcaps">dspan>-idopyranose, 82%. J<sub>CHsub> and J<sub>CCsub> values were analyzed with assistance from theoretical values obtained from density functional theory (DFT) calculations. Linearized plots of the percentages of <sup>4sup>C<sub>1sub> against limiting J<sub>CHsub> and J<sub>CCsub> values in the chair forms were used to (a) determine the compatibility of the experimental J<sub>CHsub> and J<sub>CCsub> values with <sup>4sup>C<sub>1sub>/<sup>1sup>C<sub>4sub> ratios determined from J<sub>HHsub> analysis and (b) determine the sensitivity of specific J<sub>CHsub> and J<sub>CCsub> 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-<span class="smallcaps">lspan>-[6-<sup>13sup>C]idopyranosiduronic acid and methyl α-<span class="smallcaps">dspan>-[6-<sup>13sup>C]glucopyranosiduronic acid were measured as a function of solution pH. The ring conformational equilibrium is pH-dependent in the iduronic acid.