The totally enantiocontrolled preparation of C 2 -symmetrical and pseudosymmetrical sulfur-tethered bis(amino alcohols) from anti-3-amino-1,2-alkane diols is described. The key step in the synthetic procedure involves the use of triphenylsilanethiol as a sulfide or hydrogenosulfide equivalent in the regioselective nucleophilic ring opening of both anti- and syn-aminoalkyl epoxides.