Brewster M E, Huang M J, Pop E, Pitha J, Dewar M J, Kaminski J J, Bodor N
Center for Drug Discovery, College of Pharmacy, University of Florida, Gainesville 32610.
Carbohydr Res. 1993 Apr 7;242:53-67. doi: 10.1016/0008-6215(93)80021-6.
Chemical reactivity and other characteristics of alpha-D-glucopyranose and beta-maltose were evaluated within a semiempirical molecular orbital (AM1) framework. Theoretically generated structures compared well to those determined by X-ray crystallographic techniques. Calculations suggested that the secondary hydroxy functions (OH-2 and OH-3) of the mono- and di-saccharides were more acidic than the primary alcohol (OH-6), which is consistent with experimental findings. In addition, the enhanced reactivity of the OH-3 locus, which is observed upon OH-2 alkylation of the object sugars, was rationalized in terms of increased OH-3 acidity. The chemical behavior of the monomers examined may be insightful in explaining the reactivity of glucopyranose polymers.
在半经验分子轨道（AM1）框架内评估了α-D-吡喃葡萄糖和β-麦芽糖的化学反应性及其他特性。理论生成的结构与通过X射线晶体学技术测定的结构吻合良好。计算表明，单糖和二糖的仲羟基官能团（OH-2和OH-3）比伯醇（OH-6）酸性更强，这与实验结果一致。此外，在目标糖的OH-2烷基化后观察到的OH-3位点反应性增强，可根据OH-3酸性增加来解释。所研究单体的化学行为对于解释吡喃葡萄糖聚合物的反应性可能具有启发性。
