Arylbis(arylthio)sulfonium salts have been used to activate glycals towards nucleophilic addition to form principally 2-deoxy-/I-glycosides. This method was applied to the synthesis of the 2-(methylphenylthio)_2'-phenylthio derivative (22) of methyl 0_(4-0-benxyl-2,6dideoxy-@-o-arabino-hexopyranosyll-(l -+ 3)-3,4-di-O-benzyl-S6-dideoxy-2,6?B-D-amnoside, the C'D' ring analog of an aureolic acid disaccharide. The condensation of l,S-anhydro-2,6-dideoxy-n-u&Go-hex-l-enitol with methanol in the presence of the phenylbis(phenylthio)sulfonium salt resulted in formation of the first P-glycoside linkage. The methyl 6-deoxyglucoside obtained was deprotected at HO-3 to give the 2-thiophenyl-substituted 2,6dideoxy-#I-glucoside. This was coupled with 1,5-anhydro-3,4-di-0-benzyl-2-deoxy_Darabohex-l-enitol in the presence of 4-methylphenyl[bis(4-methylphenyl)thio]sulfonium salt to give the (l-+3)-linked disaccharide 22. Finally, desulfurization of 22 using WI1 Raney nickel generated the required 2,2'-dideoxydisaccharide.