Generation of alkoxycarbenium ion pools from thioacetals and applications to glycosylation chemistry.

[reaction: see text] Alkoxycarbenium ions have been generated and accumulated as "cation pools" by the low-temperature electrochemical oxidation of alpha-phenylthioethers. Although an unsuccessful attempt to accumulate glycosyl cations was made, a one-pot method for electrochemical glycosylation, which involves anodic oxidation of thioglycosides to generate glycosyl cation equivalents followed by their reactions with glycosyl acceptors, has been developed.