Regioselective silylation of α-cyclodextrin withtert-butyl-dimethylsilyl chloride inN, N-dimethylformamide in the presence of imidazole gave, in 75% yield, the hexakis(6-O-tert-butyldimethylsilyl) derivative 2, which was transformed into the hexakis(2,3-di-O-methyl, 6-O-methyl, 2,3-di-O-propyl, and 2,3-di-O-acetyl) derivatives. On methanesulfonylation and p-toluenesulfonylation, the hexakis(2,3-di-O-acetyl) derivative16afforded the hexakis(2,3-di-O-acetyl-6-O-methylsulfonyl17and 2,3-di-O-acetyl-6-O-p -tolylsulfonyl18) derivatives, respectively. Nucleophilic displacement of17and18with iodide, bromide, chloride, and azide ions afforded the hexakis(6-deoxy-6-iodo19, 6-bromo-6-deoxy, 6-chloro-6-deoxy, and 6-azido-6-deoxy) derivatives, respectively, of α-cyclodextrin dodeca-acetate. The hexakis (2, 3-di-O-acetyl-6-deoxy) derivative was prepared from19. Selective glucosylation of16with 2,3,4,6-tetra-O-benzyl-α-D-glucopyranosyl bromide under catalysis by halide ion, followed by removal of protecting groups, furnished 6-O-α-D-glucopyranosyl-α-cyclodextrin.