Reduction of 2,3-anhydro-4,6-O-benzylidene-α-D-mannopyranosyl 2,3-anhydro-4,6-O-benzylidene-α-D-mannopyranoside with lithium aluminium hydride afforded, in high yield, the 3,3′-dideoxy-derivative arising from trans-diaxial rupture of the two epoxide rings. The dideoxy-derivative was converted into the following disaccharides by procedures involving nucleophilic displacement reactions: 6-amino-3,6-dideoxy-α-D-arabino-hexopyranosyl 6-amino-3,6-dideoxy-α-D-arabino-hexopyranoside, 3,6-dideoxy-α-D-arabino-hexopyranosyl 3,6-dideoxy-α-D-arabino-hexopyranoside, and 4,6-diacetamido-3,4,6-trideoxy-α-D-lyxo-hexopyranosyl 4,6-diacetamido-3,4,6-trideoxy-α-D-lyxo-hexopyranoside. Extensive use of 1H n.m.r. spectroscopy was made for structural elucidation.