Selective transformations of the free hydroxyl groups in 2,3,4,3′,4′-penta-O-benzyl-sucrose (1) were studied. Oxidation of1with the Swern reagent followed by reaction with Ph3P=CH-COOMe gave 2,3,4,3′,4′-penta-O-benzyl-1′,6,6′-tris-(E)(C-carbomethoxy-methylene)sucrose (2) in ca.40% as the single product. Reaction of1withp-nitrobenzoic acid under Mitsunobu conditions gave 6,6′-di-O-p-nitrobenzoyl-2,3,4,3′,4′-penta-O-benzylsucrose (3) which was easily converted into 2,3,4,3′,4′-penta-O-benzyl-1′-methoxy-methylsucrose (5). Reaction of1with one equivalent of pivaloyl chloride gave monoprotected 2,3,4,3′,4′-penta-O-benzyl-6′-O-pivaloylsucrose (6) [30% with triethylamine or 45% yield in the presence of (Bu3Sn)2O] together with a small amount of diprotected 2,3.4,3′,4′-penta-O-benzyl-6,6′-di-O-pivaloylsucrose (7).