| The synthesis of 2-deoxy-2-fluoro-D-glucose from D-arabinose was achieved through the intermediacy of 1,2-anhydro-3,4:5,6-di-0-isopropylidene-1-C-nitro-D-mannitol. The opening of the epoxide ring by anhydrous potassium hydrogen fluoride afforded 2-deoxy-2-fluoro-3,4:5,6-di-0-isopropylidene-aldehydo-D-glucose from which 2-deoxy-2-fluoro-D-glucose was obtained by hydrolysis with one of boron trichloride, trifluoroacetic acid, or boron tris (trifluoroacetate).;The synthesis of (1E, 5E)-1,2,5,6-tetradeoxy-3,4-O-isopropylidene-1,6-di-C-nitro-D-threo-hex-1,5-dienitol from D-mannitol was accomplished.;Methyl 5-deoxy-2,3-0-isopropylidene-(alpha)-D-lyxo-hexofuranoside was obtained by the reaction of either methyl 5,6-anhydro-2,3-0-isopropylidene-6-C-nitro-(alpha)-D-mannofuranoside or -(beta)-L-gulofuranoside with sodium borohydride. This same reaction was used to prepare 2-deoxy-3,4:5,6-di-0-isopropylidene-D-arabino-hexitol from either 1,2-anhydro-3,4:5,6-di-0-isopropylidene-1-C-nitro-D-mannitol or -D-glucitol.;1,2-Anhydro-3,4:5,6-di-0-isopropylidene-1-C-nitro-D-mannitol and -D-glucitol underwent selective hydrolysis of only the 5,6-acetal groups by treatment with aqueous acetic acid at 50(DEGREES). However, these two (alpha)-nitroepoxide derivatives underwent complete hydrolysis to D-glucose and D-mannose, respectively, by treatment with water at 100(DEGREES) in the presence of strong acid generated in situ.;The synthesis of methyl 5,6-anhydro-2,3-0-isopropylidene-6-C-nitro-(alpha)-D-mannofuranoside and -(beta)-L-gulofuranoside were achieved by the epoxidation of methyl (E)-5,6-dideoxy-2,3-O-isopropylidene-6-C-nitro-(alpha)-D-lyxo-hex-5-enofuranoside and methyl (Z)-5,6-dideoxy-2,3-0-isopropylidene-6-C-nitro-(alpha)-D-lyxo-hex-5-enofuranoside, respectively.;A number of necleoside (alpha)-nitroolefins and nucleoside (alpha),(beta)-unsaturated ester derivatives have been synthesized. The nucleoside (alpha)-nitroolefins were obtained by the addition of nitromethane, under alkaline conditions, to nucleoside 5'-aldehydes and treatment of the resulting epimeric mixtures of nitro alcohols with methanesulfonyl chloride-triethylamine. The nucleoside (alpha),(beta)-unsaturated ester derivatives were prepared by the reaction of the respective nucleoside 5'-aldehydes with the stabilized Wittig reagent, carbethoxymethylenetriphenylphosphorane.;The syntheses of four carbohydrate derivatives possessing two sulfonyloxy groups are described. |
