Oxidation of methyl 4,6–O-benzylidene-2-deoxy-α-L-arabino-hexopyranoside (1) with ruthenium tetroxide gave the 3-ketone 2 in high yield. A Wittig reaction between methylenetriphenylphosphorane and compound 2 gave methyl 4,6-O-benzylidene-2,3-dideoxy-3-C-methylene-α-L-erythro-hexopyranoside (3), which was hydrated by the oxymercuration–demercuration procedure to afford methyl 4,6-O-benzylidene-2-deoxy-3-C-methyl-α-L-arabino-hexopyranoside (4). The reaction of compound 4 with N-bromosuccinimide gave methyl 4-O-benzoyl-6-bromo-2,6-dideoxy-3-C-methyl-α-L-arabino-hexopyranoside (5) in high yield. Treatment of compound 5 with lithium aluminium hydride followed by acid-catalyzed hydrolysis of the resultant product, gave L-olivomycose (6).