Our results indicate that the reactivity and the activation profile of thioimidate glycosyl donors vary significantly depending on the endocyclic heteroatom (N, O, S). Reactivity diminishes in accordance with the following sequence: O> S> N; and this trend stands for a majority of promoters tested. Acyclic glycosyl thioimidates were found to be generally less reactive than the respective cyclic counterparts. The difference in the reactivity was confirmed in direct ...