Methyl 6-amino-6-deoxy-α-D-glycopyranosides having the D-gluco, D-mannoand D-galactoconfigurations (1a–3a), 2-aminoethanol (4a), 1-amino-1-deoxy-D-glucitol (5a), and 1-amino-1-deoxy-4-O-β-D-glucopyranosyl-D-glucitol (6a) were transformed into the corresponding per-O-acetyl amine hydrochlorides1d–6din excellent yields by using the 2,2-(diethoxycarbonyl)vinyl group for temporary amine protection. Deprotection of the peracetylated enamines1c–6cwas effected with chlorine in chloroform and no O→N acetyl migration occurred when short reaction times were used. Treatment of1d–6dwith thiophosgene resulted in the formation of peracetyl isothiocyanates (1e–6e).