1-Deoxy-1-nitro sugars

Vasella has used deoxy-nitro sugars for the synthesis of various biologically important carbohydrates, and the radical nitromethyladon of deoxy-nitro sugars has been used for synthesis of fnictose 6-phosphate" and 6-C-methyl and 6-C-rhydroxymethyl analogiies of iV-acetylnenraitinic acid fsee Scheme7.2. ... 

Reduction of Tfertiary Nitro Sugars [26], To a boiling solution of the 2-deoxy-2-nitro-D-g/HCO-heptuIopyranose 50 (285 mg, 0.44 mmol) in 15 mL of dry benzene under... 

T. Takamoto, R. Sudoh, and T. Nakagawa, Study on nitro sugars. Part II. Synthesis of benzyl 3,5-di-0-benzyl-2-deoxy-2-nitro-a-D-xylofuranoside and its transglycosylation with alkali, Carbohydr. Res., 27 (1973) 135-140. 

Addition of Pseudohalogens to Unsaturated Carbohydrates. Part III. Synthesis of 3-Deoxy-3-C-nitromethyl-D-allose, a Branched-chain Nitro Sugar, W. A. Szarek, J. S. Jewell, I. Szczerek, and J. K. N. Jones, Can.]. Chem., 47 (1969) 4473-4476. 

As far as intermolecular, substrate-controlled additions are concerned, unsaturated nitro sugars can serve as acceptors. For example, when 3-0-acetyl-5,6-dideoxy-l,2-O-isopropylidene-6-nitro-a-D-. v7o-hexofuranos-5-ene (8) was treated with methanolic sodium hydroxide, 3-0-acetyl-6-deoxy-l,2-O-isopropylidene-5-0-methyl-6-nitro-D-glucofuranose (9) and L-/cfo-furanose (10) were formed in a ratio of ca. 4 1 (estimated by TLC, no isolated yields reported)59. Upon prolonged reaction, additional deacetylation was observed. 

MacDonald and Fischer prepared D- fluco-hexodialdose (27) by two different methods. By use of the Nef reaction, 6-deoxy-l,2-0-isopropyli-dene-6-nitro-n-glucose (26) was converted into the dialdose (27), which was isolated from the aqueous solution as its insoluble, crystalline bis-(diethyl dithioacetal) (in 48% yield, after recrystallization). It is of interest to note that the starting material (26) is one of the two isomeric 6-deoxy-6-nitro sugars which Grosheintz and Fischer prepared from 1,2-0-iso-propylidene-a-D-x2/lo-pentodialdo-l, 4-furanose (7). Thus, the synthesis discussed here is an ascent from a pentodialdose to a hexodialdose. 

Deoxy-6-nitro-D-glucose (90) and 6-deoxy-6-nitro-L-idose (91) were the first reducing nitro sugars to be synthesized.98 Nitromethane addition to 1,2-O-isopropylidene-a-D-xy/o-pentodialdo-1,4-furanose (87) produced a mixture of 6-deoxy-l,2-0-isopropylidene-6-nitro-a-D-glucofuranose (88) and -j8-L-idofuranose (89). These C-5 epimers could be separated by reaction with acetone, whereby 89 gave a l,2 3,5-di-isopropylidene acetal more readily than did 88. Acid hydrolysis of the acetone groups then afforded 90 and 91. 

From Nitro-sugars. - The 2-acetamido-2-deoxy-p-D-galactopyrano-sylamine 25 was obtained by addition of benzimidazole to a 2-nitro-galactal derivative (see Chapter 10). ... 

The peracetylated 1-deoxy-l-nitro-sugars gave 1-C-nitroglycals either spontaneously or on base-catalyzed 6-ellminatlon, as shown for the 1-C-nltroglucal (15) in Scheme 5. Addition of ammonia or amines to some of these 1-C-nltroglycals gave 2-amino-2-deoxy-l-C-nltrohexose derivatives with an axial C-2 substituent, e.g . the 2-acetamldo-2-deoxy-D-mannose derivative (I6) (Scheme 6). ... 

Anhydromaltose has been converted to the pseudo-disaccharides (25) containing 3-amino-3-deoxy-epz-inositol or 1-amino-l-deoxy-l-L-myo-inositol via the 6-deoxy-6-nitromaltose derivative (26). The branched-chain unsaturated 6-nitro-sugar (27), prepared conventionally from D-glucose, yielded isomeric dithianyl adducts which were similarly cyclized to give the nitro-cyclitols (28) and (29), of interest as potential intermediates for the synthesis of tetrodo-... 

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