Synthesis of dibekacin analogs containing 3-oxaand 3-aza-2,3,4-trideoxy-d-glycero-hexopyranose

6-O-(3-Oxa-2,3,4-trideoxy-α-d-glycero-hexopyranosyl) derivatives (10 and 17) of both 3′,4′-dideoxyneamine and 5-epifluoro-5,3′,4′-trideoxyneamine have been prepared by coupling ethyl 6-O-benzyl-3-oxa-2,3,4-trideoxy-1-thio-d-glycero-hexopyranoside (5) with suitable aglycons. The corresponding 3″-aza derivative (19) of dibekacin (6) was prepared by oxidation of 1,3,2′,6′-tetra-N-tosyldibekacin (7) with Pb(OAc)4 followed by treatment with NH4OAc and reduction with NaBH3CN. Related ring-opening compounds (11 and 25) were also prepared.