Glucose 3-deoxy-3-nitro

Aliphatic fluorodenitration has also been applied to mononitro compounds, specifically to an a-nitroepoxide Thus, l,2-anhydro-3 4 5,6-di-O isopropyli dene-1-C-nitro D mannitol and labeled potassium bifluonde give 2-deoxy-2-fluo-ro-3,4 5,6-di-O-isopropylidene aldehydo D glucose [J03, 104] (equation 30)... 

A mixture of methyl 3-deoxy-3-C-methyl-3-nitro-ct-D- and fi-L-glucopyranosides d l is formed by the reaction of nitroethane with the sugar thaldehyde obtained from L-glucose The products are separated and converted into branched-chain fluoro nitro l- and L-sugars fEq 361 ... 

In extending this direct method of synthesis, we next investigated the possibility of preparing similarly constituted halides from 2-deoxy-D-arabino-hexose (2-deoxy-D-glucose) (21). The hexose was subjected to a partial anomerization procedure described by Bergmann and co-workers (1). The solid material obtained by this procedure is a mixture of the anomeric forms of 2-deoxy-D-arabino-hexose low temperature p-nitro-benzoylation of the latter in pyridine resulted in a mixture of crystalline, anomeric tetrakis-p-nitrobenzoates in a ratio of approximately 1 1. They were readily separable by fractional recrystallization, and treatment of either with an excess of hydrogen bromide in dichloromethane, or with... 

In analoger Weise erhalt man aus o-Glucose in 95%iger Ausbeute 112 5,6-Bis-O-isopro-pyliden-3-nitro-3-deoxy-oL-T>-allofuranose2 ... 

H5C CH2 0- . HsCg - CH2 - 0OH H5C8 — CH2 NH- OH o-ch2-c6h5 NO, 2,3,4,6-Tetra-O-benzyl-l-deoxy-l-nitro- glucose 90... 

Deoxy-D-glucose 5,6-O-Isopropyli-den-l-(nitro-methyl)- E2le, 4851 (OH CH2-N02)... 

S YNS 1 -(2-CHLOROETHYL)-3-(d-GLUCOPYRANOS-2-YL)-l-NITROSOUREA 2-((((2-CHLOROETHYL)NITRO-SOAMINO)CARBONYL)AMINO)-2-DEOXY-d-GLUCOPYRANOSE 2-((((2-CHLOROETHYL)NITROSO-AMINO)CARBONYL)AMINO)-2-DEOXY-d-GLUCOSE 2-(3-(2-CHLOROETHYL)-3-NITROSOUREIDO)-2-DEOXY-d-GLUCOSOPYRANOSE 2-(3-(2-CHLOROETHYL)-3-NITROSOUREIDO)-d-GLUCO-PYRANOSE CHLZ CZT DCNU NSC-178248 NSC-D 254157... 

An intriguing and important adaptation of the aldose-nitromethane reaction was also studied in Toronto by Fischer and Jean Grosheintz. By addition of nitromethane to 1,2-0-isopropylidene-n-a 2/fo-pentodialdose and subsequent hydrolysis of the acetone group, they obtained a mixture of 6-deoxy-6-nitro-D-glucose and 6-deoxy-6-nitro-L-idose. A second, intramolecular reaction of these substances led to a mixture of deoxynitro-inositols and, by reduction, to the related aminodeoxyinositols. One of the latter was successfully deaminated a few years later, by T. Posternak, to the B-vitamin, mt/o-inositol (12), thus completing a synthesis of the latter that started from n-glucose. 

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. 

Grosheintz and Fischer synthesized the 6-deoxy-6-nitro derivatives of D-glucose and L-idose by treating l,2-0-isopropylidene-a-D-a i/lo-pento-dialdo-l,4-furanose with nitromethane, and employed these sugars for cyclization to cyclitol derivatives. These reactions and their importance in cyclitol chemistry have already been reviewed in this Series. - ... 

In addition to providing a synthetic pathway68 to kanosamine, a component of kanamycin, the convenient availability of 40 and 41 has stimulated a great deal of research that will be discussed in subsequent Sections. Acid hydrolysis of 40 furnished 3-deoxy-3-nitro-D-glucose, the only reducing 3-deoxy-3-nitroglycose known so far (see Section IV,lc p. 118). 

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. 

Free 3-deoxy-3-nitro-D-glucose was obtained151 by hydrolysis of its methyl /3-D-pyranoside (40) with 5 M hydrochloric acid for 90 min at 100°. These conditions appear to be somewhat more strenuous than those required for hydrolysis of ordinary hexopyranosides. On the other hand, debenzylidenation of 2-O-acetyl,04 2-deoxy,64 85,80 152 2-acetamido-2-deoxy,155 and 2-O-alkyl149,156 derivatives of methyl 4,6-0-... 

Another application of alkoxylation of nitro-olefins is in the synthesis of positional isomers of muramic acid.156 Addition of isopropyl L-lactate or isopropyl D-lactate to 141 led to the side-chain epimers 199 and 200, respectively, in yields of over 80%. When isopropyl dl-lactate was used, 199 and 200 were obtained as a mixture in which, interestingly, the former preponderated. Removal of protecting groups, reduction, and derivation furnished various derivatives of 3-amino-2-0-[D(and L)-l-carboxyethyl]-3-deoxy-D-glucose (201). 

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