3-deoxy-2-0-ethyl-3-nitro

Ethyl 2-acetamido-2-deoxy-l-thio-a-D-glucofuranoside (103) was oxidized with lead tetraacetate to the partially protected dialdose (104), which, with nitromethane, gave a mixture of the 5-epimeric 6-nitro thioglycosides (105). The 2-acetamido-2,6-dideoxy-6-nitro-hexoses (106) produced therefrom by desulfurization with mercuric chloride were not separated, but were cyclized immediately, in the presence of barium hydroxide, to a mixture of l-acetamido-l,3-di-deoxy-3-nitroinositol salts (107). Acidification, hydrogenation, and acetylation then afforded 108 (and a stereoisomer). 

Fusion procedures have also been used to prepare nucleosides of 3-nitro-l,2,4-triazole and ethyl 4-nitropyrazole-3-carboxylate. Epimerization at C-2 occurred during the fusion of 3-acetamido-l,2,5-tri-0-acetyl-3-deoxy-j8-D-ribofuranose with 2,6-dichloropurine, yielding some a- and )3-D-arabinofuranosyl derivatives in addition to the expected products. ... 

Whereas cyclization of aldohexose and aldoheptose proceeded septanoside formation, implementing aldol-type condensation was also devised to derive septanoside systems. An early report by Baschang illustrated that a dialdehyde, such as 17, obtained by periodate oxidation of a pyranoside, upon Knoevenagel condensation afforded 3-deoxy-3-nitroseptanoside 18 (Scheme 13.5a) [16], On the contrary, such a reaction on dialdehyde 19 with ethyl nitroacetate afforded hij-nitro-septanoside derivatives 20 and 21 (Scheme 13.5b) [17]. 

Nitromethane added to a soln. of D -methoxy-D-hydroxymethyldiglycolic aldehyde in abs. methanol, then a chilled soln. of Na in methanol added dropwise with swirling to the ice-cooled soln., and kept 15 min. in the ice bath methyl Na-3-aci-nitro-3-deoxy-hexapyranoside (Y 79-85%) added to a powdered mixture of KHSO4 and Na2S04 in a ball-mill, milled 30 min., and extracted with ethyl acetate mixture of methyl 3-nitro-3-deoxy-a-hexopyranosides containing a major amount of methyl 3-nitro-3-deoxy-a-D-mannopyranoside (Y 84 to 90%). H. H. Baer and H. O. L. Fischer, Am. Soc. 82, 3709 (1960). 

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