Synthesis of Thiadiazolylaminoglycosides Through Ring Contraction of Triazinoglycosides Induced by [TBA‐Ox]

A new synthetic route to thiadiazolylaminoglycosides, by a ring expansion/ring contraction sequence of glycosyl triazines, has been developed. Two potential mechanisms of this oxidative ring contraction using [TBA-Ox] are discussed. The more plausible involves formation of an oxatriazepane intermediate followed by loss of formic acid, ring opening, and subsequent recyclization.