Reactivity, Selectivity, and Synthesis of 4-C-Silylated Glycosyl Donors and 4-Deoxy Analogues

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.