2012
DOI: 10.1021/jp303183y
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Dependence of Pyranose Ring Puckering on Anomeric Configuration: Methyl Idopyranosides

Abstract: In the aldohexopyranose idose, the unique presence of three axial ring hydroxyl groups causes considerable conformational flexibility, rendering it challenging to study experimentally and an excellent model for rationalising the relationship between puckering and anomeric configuration. Puckering in methyl α- and β-l-idopyranosides was predicted from kinetically rigorous 10 μs simulations using GLYCAM11 and three explicit water models (TIP3P, TIP4P and TIP4P-EW). In each case, computed pyranose ring three-bond… Show more

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Cited by 36 publications
(71 citation statements)
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References 38 publications
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“…Compared to the experimental results of Ref. for α‐ and β‐Ido (−3.4 and 2.7 kJ mol −1 , respectively), a positive shift is indeed observed for the α‐anomer and a negative one for the β‐anomer, albeit of a smaller magnitude than suggested by 56A6 CARBO_R . The ΔF i values calculated using the force field are 7.5 and 4.5 kJ mol −1 , respectively, which means, in particular, that although 56A6 CARBO_R correctly predicts a dominant 1 C 4 chair for α‐Ido, it is apparently at odd with experiment in predicting a dominant 4 C 1 chair for α‐Me‐Ido.…”
Section: Resultscontrasting
confidence: 55%
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“…Compared to the experimental results of Ref. for α‐ and β‐Ido (−3.4 and 2.7 kJ mol −1 , respectively), a positive shift is indeed observed for the α‐anomer and a negative one for the β‐anomer, albeit of a smaller magnitude than suggested by 56A6 CARBO_R . The ΔF i values calculated using the force field are 7.5 and 4.5 kJ mol −1 , respectively, which means, in particular, that although 56A6 CARBO_R correctly predicts a dominant 1 C 4 chair for α‐Ido, it is apparently at odd with experiment in predicting a dominant 4 C 1 chair for α‐Me‐Ido.…”
Section: Resultscontrasting
confidence: 55%
“…To our knowledge, the only experimental results available for the ring‐conformational equilibrium of an O 1 ‐methyl‐hexopyranoside concern α‐Me‐Ido and β‐Me‐Ido, where population ratios inferred from NMR J ‐coupling constants ( 4 C 1 : 1 C 4 ratios of 35:65 and 76:24, respectively, see Supporting Information of the indicated reference, Table S8; the ratios provided for the l ‐compound in the two‐site rigid model have been inverted here to be representative for the d ‐compound) suggest chair‐inversion free energies of −1.1 and 2.6 kJ mol −1 , respectively. Compared to the experimental results of Ref.…”
Section: Resultsmentioning
confidence: 98%
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“…This flexibility leads to observed vicinal coupling constants that are averaged over the constants of the corresponding conformers. Thus, the coupling constants of 14 and 2 are significantly higher than the calculated values for methyl β‐ l ‐idopyranoside ( 3 J H3‐H4 = 3 J H3‐H2 =3.0 Hz) in the favored 1 C 4 conformation . Similar conformational flexibility could already be demonstrated for the gem ‐difluorocarba‐sugar analog of methyl‐β‐ l ‐idopyranoside .…”
Section: Resultssupporting
confidence: 66%
“…While the ring flip dynamics were not captured by this work, long timescale simulations of IdoA using GLYCAM have previously shown experimentally consistent ring populations. 53 The 3 J HH coupling analysis also suggested that the terminal GlcA ring may not exclusively adopt the expected 4 C 1 conformation.…”
Section: Discussionmentioning
confidence: 99%