The role of lone pair interactions in the chemistry of the monosaccharides. The mechanisms of the oxidations of monosaccharides by bromine, chromium trioxide in acetic acid, and ozone

The molecular modeling program STR3DI32.EXE and its molecular mechanics module quantized valence bondsʹ molecular mechanics (QVBMM) were used to simulate the stereo-electronic effects present in the conformers of 2-hydroxypyran, 2-methoxypyran and the 1,8-dioxadecalins in order to evaluate the relative energies and hence nucleophilicities of their anomeric lone pairs. The derived data were not only completely congruent with the experimental evidence, but also offered refinements to previous rationalizations of these intriguing oxidative reactions of acetals and Ahemiacetals.