Department of Organic Chemistry, Arrhenius Laboratory, Stockholm University, S-106 91, Stockholm, Sweden.
Sussex Research Laboratories Inc., 100 Sussex Drive Suite 1120B, Ottawa, Ontario, K1A 0R6, Canada.
Carbohydr Res. 2024 Jan;535:109010. doi: 10.1016/j.carres.2023.109010. Epub 2023 Dec 13.
Methodology development in carbohydrate chemistry entails the stereoselective formation of C-O bonds as a key step in the synthesis of oligo- and polysaccharides. The anomeric selectivity of a glycosylation reaction is affected by a multitude of parameters, such as the nature of the donor and acceptor, activator/promotor system, temperature and solvent. The influence of different solvents on the stereoselective outcome of glycosylation reactions employing thioglucopyranosides as glycosyl donors with a non-participating protecting group at position 2 has been studied. A large change in selectivity as a function of solvent was observed and a correlation between selectivity and the Kamlet-Taft solvent parameter π* was found. Furthermore, molecular modeling using density functional theory methodology was conducted to decipher the role of the solvent and possible reaction pathways were investigated.
碳水化合物化学中的方法学发展需要立体选择性地形成 C-O 键，这是寡糖和多糖合成中的关键步骤。糖苷化反应的端基选择性受多种参数的影响，例如供体和受体的性质、活化剂/促进剂系统、温度和溶剂。研究了不同溶剂对采用硫代葡萄糖吡喃糖苷作为糖基供体、在 2 位具有非参与性保护基的糖苷化反应的立体选择性结果的影响。观察到选择性随溶剂的变化很大，并发现选择性与 Kamlet-Taft 溶剂参数 π*之间存在相关性。此外，还使用密度泛函理论方法进行了分子建模，以破译溶剂的作用，并研究了可能的反应途径。
