The reaction of 2,3-O-isopropylidene-D-glyceraldehyde with different dialkyl and diarylthiomethyl sulfoxides occurs with a high selectivity and produces the corresponding 1-alkyl(or 1-aryl)-sulfynil-1-alkyl(or 1-aryl) thio-3,4-O-isopropylidene-D-tetroses as pure diastereoisomers. We have determined the absolute configuration of the three chiral centers formed in these reactions.