Abstract A couple of enantiomeric octopyranoses, endowed with differentiated protective groups, namely the L-threo-D-talo-and D-threo-L-talo- octose derivatives L-6 and D-6, were synthesized from the enantiomers of threose L-1 and D-1 in ca 10% overall yield in five individual steps. The synthetic plan emphasizes the value of 2-(trimethylsiloxy)furan (TMSOF) as four-carbon homologative reactant of homochiral aldehyde precursors en route to higher-carbon monosaccharide units.