Department of Chemistry, University of Copenhagen, Universitetsparken 5, 2100, Copenhagen Ø, Denmark.
Current address: School of Chemistry, University College Dublin, Belfield, Dublin 4, Ireland.
Angew Chem Int Ed Engl. 2021 Feb 1;60(5):2689-2693. doi: 10.1002/anie.202009209. Epub 2020 Nov 24.
A method for introducing dimethylphenylsilyl at the 4-position in carbohydrates has been developed. Two C-silylated glycosyl donors were prepared via levoglucosenone, starting from cellulose. The glycosylation properties were studied using three glucoside acceptors, a 3-OH, 4-OH, and 6-OH. Compared with the 4-deoxy variant, it was found that the anomeric selectivity was influenced more by the C-2 substituents orientation than the silyl in the 4-position. In general, the reactivity of these donors was higher than the corresponding 4-deoxy-analogue, albeit a competition experiment showed that the introduction of a C-Si increases the relative reactivity by a modest factor of around two.
已开发出一种在碳水化合物的 4-位引入二甲基苯基硅基的方法。通过从纤维素开始的左旋葡庚酮，制备了两种 C-硅化的糖基供体。使用三种糖苷受体（3-OH、4-OH 和 6-OH）研究了糖苷化性质。与 4-脱氧变体相比，发现端基选择性受 C-2 取代基取向的影响大于 4-位的硅基。一般来说，这些供体的反应性高于相应的 4-脱氧类似物，尽管竞争实验表明，C-Si 的引入仅使相对反应性适度增加约两倍。
