Three disaccharides (13, 16, and 20), compounds to be utilized in the preparation of analogs of the anticancer agent mithramycin (1), have been synthesized from appropriately protected 2,6-dideoxy sugars. In these syntheses triflate rearrangement was used to invert configuration at specific chiral centers. Silver-silicate controlled reaction generated the desired β-linkages between saccharide units. Silver-silicate also catalyzed β-glycoside formation when the glycosyl bromides derived from 13 and 20 each were coupled witho-methylphenol (a model aglycon).