Expanding 1-Aminosugar Synthesis through Activated Glycals’ Reactivity

Glycal family offers an interesting platform whose reactivity let the possibility to reach diverse glycoanalogues. In particular, the Ferrier rearrangement allows the introduction of diverse nucleophiles on the anomeric position but stays limited with regard to the nitrogen-containing nucleophiles, which can be possibly used with success. Herein, we utilize peracetylated C2-substituted glycal substrates to achieve Ferrier-type 1-aminoglycoside compounds under activator-free conditions, resulting in moderate to good yields and good to excellent β-selectivity. Various secondary amines have been successfully employed. We explored the influence of C2-substitution (electron-withdrawing character) and glycal configuration, synthesizing 20 different 1-aminoglycosides through this method.