Synthesis of Streptolidine from d-Xylose

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Abstract
An alternative total synthesis of streptolidine (roseonine, geamine) was achieved starting from d-xylose. Direct azidolysis of methyl 2,3,5-tri-O-mesyl-α-d-xylofuranoside (6a) afforded methyl 2,3,5-triazido-2,3,5-trideoxy-α-d-arabinofuranoside (9a), whereas the β-anomer of 6a gave only 3,5-diazido-3,5-dideoxy-2-O-mesyl-β-d-ribofuranoside (8b) indicating that the glycosidic configuration in the furanoside system has a decisive influence on the reactivity of the 2-mesyloxy group. However, the β-anomer of diazide (8b) was anomerized to α-anomer which readily undergoes azidolysis to give the triazide (9a). The triazide was successively hydrogenated, benzyloxycarbonylated, and then hydrolyzed to give 2,3,5-tris(benzyloxycarbonylamino)-2,3,5-trideoxy-d-arabinofuranose, which was identical with that prepared from d-ribose. Streptolidine could be synthesized from this key intermediate.