Straightforward S-S bond formation via the oxidation of S-acetyl group by iodine was reported here. The reaction was further applied in the synthesis of per-O-acetylated glycosyl disulfides. These studies demonstrated great improvement in reaction rate, yield, and general convenience in the presence of N-iodosuccinimide. Furthermore, selectively deacetylated glycosyl thiols were obtained in high yields when these per-O-acetylated glycosyl disulfides were reduced with tris(2-carboxyethyl)-phosphine (TCEP). Our method supplied an efficient way to obtain both per-O-acetylated glycosyl disulfides and per-O-acetylated glycosyl thiols in which the sulfur group was located at any position.

We herein developed an efficient method for removing thioacetyl to synthesize acylated deoxy glycosides in a one-pot reaction, where the thioacetyl was selectively deacetylated by hydrazine hydrate in DMF within 2–5 min at room temperature, followed by desulfurization under UV light for 1–2 h in the presence of TCEP·HCl. The method was then used to synthesize 2-deoxy glycosides with absolute α/β-configuration via stereoselective control of C-2 thioacetate in glycosylation.