6-Nitro-6-desoxy-D-glucose

J. M. Grosheintz and H. O. L. Fischer, Synthesis of 6-nitro-6-desoxy-D-glucose and 6-nitro-6-desoxy-L-idose, J. Am. Chem. Soc., 70 (1948) 1476-1479. 

These isomeric acetonated nitrodesoxy sugars could not be separated by fractional crystallization but a selective re-acetonation of the mixture gave mainly the di-isopropylidene derivative of the nitrodesoxy-L-idose, which then could be separated readily from the unchanged mono-iso-propylidene nitrodesoxy-D-glucose. Hydrolysis of the isopropylidene substituents with dilute acid then gave, respectively, 6-nitro-6-desoxy-L-idose and 6-nitro-6-desoxy-D-glucose. 

Thus, either of the nitrodesoxy sugars may be expected to give a mixture containing any of eight possible diastereoisomeric nitrodesoxy inositols. Actually, three individual nitrodesoxy inositols were isolated, and all three were obtained from the cyclization of either 6-nitro-6-desoxy-D-glucose or 6-nitro-6-desoxy-L-idose. 

N 6.70%. A mixt of nitrodesoxyinositols was obtd by cyclization of 6-ftitro-o-desoxy-D-glucose, of 6-nitro-6-desoxy-L-idose or of an equimolar mixt of the two using very small amts of alkali Nitrodesoxyinositol l, crysts (from dioxane), mp 147-48° insol in acet... 

The method was used successfully initially for the preparation of 2-desoxy-D-glucose.4 D-Arabinose was treated with nitromethane in the presence of sodium methoxide and gave a mixture of 1-nitro-l-desoxy-D-mannitol (XXXV) and 1-nitro-l-desoxy-D-glucitol (XXXVI). The mixture was not separated, but was acetylated and subsequently treated with bicarbonate to convert it into D-arabo-3,4,5,6-tetraacetoxy-1 -nitro-... 

A new synthetic approach to D-ribose has recently been made by Sowden.43 In this procedure 4,6-benzylidene-D-glucose (X) was reduced catalytically to 4,6-benzylidene-D-glucitol (XI) which was then oxidized with sodium metaperiodate to 2,4-benzylidene-D-erythrose (XII). Condensation of this latter compound with nitromethane gave a mixture of epimeric, crystalline, substituted C-nitro alcohols, 3,5-benzylidene-1-desoxy-l-nitro-D-arabitol and 3,5-benzylidene-l-desoxy-l-nitro-D-ribitol (XIII). After separation, the appropriate isomer was hydrolyzed to 1-nitro-l-desoxy-D-ribitol (XIV) which, in the form of its sodium salt was decomposed directly to D-ribose (XV), isolated as its benzylphenyl-hydrazone. This synthesis is of interest in that it may be used to obtain D-ribose labeled at carbon 1 with C.14... 

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