Deoxyfluoroketohexoses: 4-deoxy-4-fluoro-D-sorbose and -tagatose and 5-deoxy-5-fluoro-L-sorbose.
4-Deoxy-4-fluoro-alpha-D-sorbose (6) was prepared in crystalline form by the action of potassium hydrogen fluoride on 3,4-anhydro-1,2-O-isopropylidene-beta-D-psicopyranose (3) followed by deacetonation.  Under identical conditions, 3,4-anhydro-1,2-O-isopropylidene-beta-D-tagatopyranose (7) underwent epoxide migration to give 4,5-anhydro-1,2-O-isopropylidene-beta-D-fructopyranose (12), which after deacetonation yielded 4-deoxy-4-fluoro-D-tagatose (15) and 5-deoxy-5-fluoro-alpha-L-sorbopyranose (16), the latter as the crystalline, free sugar.  The action of glycol-cleavage reagents on the isopropylidene acetals of the deoxyfluoro sugars was consistent with the assigned structures.  The structures were established by 13-C n.m.r. studies of the free deoxyfluoro sugars 6 and 16 and of the isopropylidene acetal 13, and by 1-H n.m.r. studies on the acetylated isopropylidene acetals 5 diacetate, 13 diacetate, and 14 diacetate.  5-Deoxy-5-fluoro-L-sorbose (16) was biologically active, producing in mice effects characteristic of deoxyfluorotrioses and of fluoroacetate.  4-Deoxy-4-fluoro-D-tagatose (15) and 4-deoxy-4-fluoro-D-sorbose (6) produced no apparent effects in mice up to a dose of 500mg/kg.  The implications of these findings with respect to transport, phosphorylation, and the action of aldolase on ketohexoses are discussed.
D000970:Antineoplastic Agents; D003837:Deoxy Sugars / Q000138:chemical synthesis* / Q000627:therapeutic use; D005461:Fluorine / Q000627:therapeutic use; D006601:Hexoses / Q000627:therapeutic use; D007928:Lethal Dose 50; D008968:Molecular Conformation; D009369:Neoplasms / Q000188:drug therapy; D013013:Sorbose / Q000627:therapeutic use
D000970:Antineoplastic Agents; D003837:Deoxy Sugars; D006601:Hexoses; D005461:Fluorine; D013013:Sorbose