Synthesis of dibekacin analogs containing 3-oxa- and 3-aza-2,3,4-trideoxy-D-glycero-hexopyranose.

6-O-(3-Oxa-2,3,4-trideoxy-alpha-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.