Upon reaction with sodium nitrite, the corresponding triflate2of known 1,3,4,6-tetra-O-pivaloyl-β-d-fructofuranosyl 2,3,6-tri-O-pivaloyl-α-d-glucopyranoside (1), afforded thegalacto-sucrose3in high yield. This compound was converted into 4-deoxy-4-fluorosucrose derivative4by treatment with DAST. The reaction of triflate6, derived from3, with lithium azide afforded 4-azido-4-deoxysucrose derivative7which was transformed into 4-amino-4-deoxysucrose9. SN2 Displacement of the triflate of compound6with thioacetate ion provided the expected 4-S-acetyl-4-thiosucrose derivative10in excellent yield. Deacetylation of10afforded a mixture of 4-thiosucrose11and 4-thiosucrose disulfide12.