Starting from methyl 4,6-O-benzylidene-2-deoxy-α-D-ribo-hexopyranoside-3-ulose1and proceeding through its corresponding tosyl-epoxide derivative2, various branched-chain sugars (3-8) were prepared by nucleophilic and reductive ring openings. The presence of the sulfonylated oxirane group was found to be compatible with chemical transformations of the benzylidene acetal group (9-11), allowing facile access to the 6-deoxyhexoses (12-13).