Idose 6-deoxy-6-nitro

The study was intended to prove the intermediacy of nitroalkene 8 in the unexpected deacetona-tion-methoxylation of 1,2 3,5-diisopropylidene-6-deoxy-6-nitro-a-n-glucofuranose(ll), which occurred upon treating the latter carbohydrate with dilute methanolic sodium hydroxide60. In this reaction, deacetylated 9 and 10 were formed in a 4 1 ratio, too. Interestingly, under identical conditions, the cpimeric L-idose 12 was reversibly deprotonated and did not lose acetone. 

Idose, 5-acetamido-5-deoxy-L-, 175 —, 5-acetamido-5,6-dideoxy-6-nitro-L-,... 

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. 

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. - ... 

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. 

D-glucose. This transformation has recently been demonstrated (32b), Synthesis in vitro is based on the work of Grosheintz and Fischer (S3). They found that 6-deoxy-6-nitro-D-glucose (or, likewise, 6-deoxy-6-nitro-L-idose) condensed in slightly alkaline solution to form two monodeoxymononitro-iiiositols. These were converted to the corresponding amines, one of which can also be obtained by reduction of the phenylhydrazone or oxime of mi/o-inosose-2 (scyllo-myo-inosose) h). The final and crucial step,... 

The synthesis of deoxynitroinositols by the base-catalysed cyclization of 6-deoxy-3-0-methyl-6-nitro-D-allose (318) and -L-talose (319) has been investigated. The products shown in Scheme 113 were formed under conditions (pH 8—9) favouring kinetic control, whereas similar equilibrium mixtures of stereoisomers were obtained from (318) and (319) in strongly alkaline solutions (pH >12) that favour thermodynamic control. A related base-catalysed cyclization of 3-0-benzyl-6-deoxy-6-nitro-D-glucose and -L-idose gave mixtures of O-benzyldeoxynitroinositols. Under conditions of kinetic control, the D- / c<7-derivative furnished mainly 6-0-benzyl-3-deoxy-3-nitro-mwco-inositol... 

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