Recently we have described1high pressure (4+2) cycloaddition of l-methoxybuta-1,3-diene (1)to 2,3-0-isopropylidene-D-glyceraldehyde (z), which gives rise to chiral cycloadducts3(Scheme). action was carried out under high-pressure conditions (22 kbar, 50°C. diethyl ether as solvent, 20 h, 80% yield)2 four diastereoisomeric adducts were formed in a ratio of 3a:3b:3c:3d=66:16:13:5. The reaction mixture was separated by column chromatography yielding two fractions which contained diastereoisomeric mixtures (3a+3b) and (3c+3d), respectively. Absolute configuration at the C-5 carbon atom in both mixtures was established by chemical correlation.' These results prompted us to use a mixture (3a+3b), being stereochemically pure at C-5 chiral center, in the synthesis of optically active methyl 4-deoxyheptosides (Scheme).