A C-2 regioselective debenzylative cycloetherification/reductive elimination sequence applied to perbenzylated C-allyl iminosugars is described. This NIS/TMSOTf-triggered deprotection was successfully applied to five-, six-, and sevenmembered C-allyl iminosugars including 1,2 cis and 1,2 trans stereoisomers. It allows rapid introduction of structural diversity at the key C-2 position in a stereoselective manner exploiting the anchimeric assistance of the intracyclic N-benzyl group, giving access to the 2-acetamido and 2-fluoro D-gluco configured C-allyl iminosugars and to the epimeric D-manno derivative.

The synthesis and glycosidase inhibition profile of a series of bicyclic analogs of DNJ and DMJ displaying a similar hydroxyl pattern and a distinct conformation is described.