The reaction of 2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyl isothiocyanate with enamines in basic medium to form the glucosylthioamides9-16, the glucosylthiourea17, and the nucleoside analogue18is reported. TheN-halogenophenyl-(1-3,5-7) and theN-(3,4-dimethoxybenzyl)-(4,8) enaminoesters or enaminones were prepared as precursors for9-18. The treatment of several of the prepared glucosylthioamides with thiophosgene yields dithioxopyrimidine nucleosides (19-22) with the sugar ring on position 3 of the heterocycle. Glucosylamides are isolated as byproducts. The enamino moieties of the prepared glucosylthioamides and glycosylamides have theEEEconfiguration and the thioamide or amide bond theZ, antigeometry.