Anomer preferences for glucuronic and galacturonic acid and derivatives and influence of electron-withdrawing substituents
Murphy, Paul V.
MetadataShow full item record
This item's downloads: 272 (view details)
Cited 6 times in Scopus (view citations)
Kerins, Louise, Byrne, Sylvester, Gabba, Adele, & Murphy, Paul V. (2018). Anomer Preferences for Glucuronic and Galacturonic Acid and Derivatives and Influence of Electron-Withdrawing Substituents. The Journal of Organic Chemistry, 83(15), 7714-7729. doi: 10.1021/acs.joc.8b0061
Equilibrium anomeric ratios are reported for pyranoses (hemiacetals) of glucuronic and galacturonic acid and their derivatives. These are compared to related gluco- and galactopyranoses and to deoxyfluorogluco- and deoxyfluorogalactopyranoses. An association between axial anomer stability and the sum of H-1 NMR downfield chemical shifts for protons H-3 and H-5 was observed in D2O with gluco- and galactopyranoses as reference compounds. When compared to 2-hydroxytetrahydropyran in water, introduction of three OAc substituents and one carboxylic acid substituent leads to an increase in stability of the axial anomer by 0.89-1.05 kcal/mol. This is interpreted as the electron-withdrawing substituents causing a reduction in the steric (gauche) interaction and an increase in favourable Coulombic interaction between CH groups of the pyranose and the anomeric group through substituent deshielding effects. Anomer preferences for galacturonic acid and its derivatives were more sensitive to solvent polarity compared to other pyranoses, and this may be linked to the electrostatic potential and reduced stabilization of the equatorial anomeric OH group due to reduced hydrogen bonding. The latter is more notable in nonpolar chloroform. Analysis of crystal structures combined with molecular dynamics indicated there are conformational distinctions between galacturonic acid and glucuronic acid that could influence properties.