Inositols deoxy-1-nitro

Deoxy-I,2-0-isopropylidenc-4-C-mcthyl-4-nitro-<-Ajr0-inositol (15) Single Procedure33 ... 

The barium hydroxide catalyzed Henry reaction of 6-deoxy-3-0-methyl-6-nilro-L-ta/r -pyra-nosc (17), generated from l,2-0-isopropylidcnc-3-0-mcthyl-o -D-r/7to-pcntodialdo-1.4-furanose (16), furnishes 5-deoxy-2-GMnethyl-5-nitro-wi o-inositol (18) in 92% yield and 90% purity1 2 3 4 5 6. 

Deoxy-chiro-inositol 1,2-0-Isopropylidene-4-C-methyl-4-nitro- E21b, 1791 (0-SiR3-6,7-dideoxy— 2,3-O-isopropyli-den — 6-N 02 — heptofuranoside/ R4NF)... 

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. 

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-... 

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... 

M Ba-hydroxide soln. added slowly under Na to an aq. soln. of 6-deoxy-3-0-methyl-6-nitro-L-talose until pH 7.9-8.7 is reached, and the product isolated after 23 hrs. at 0 -> 5-deoxy-2-0-methyl-5-nitro-myo-inositol. Y 92% purity ca. 90%. F. e. s. J. Kovaf and H. H. Baer, Carboh. Res. 45, 161 (1975). 

Amino-l-deoxy-j-cy/Zo-inositol (339) has been prepared by hydrogenolytic reduction of the corresponding 3,4-di-O-benzyl-l-deoxy-l-nitro-derivative, which was obtained by base-catalysed cyclization of 2,3-di-0-benzyl-6-deoxy-6-nitro-D-glucose. ... 

MM2 Calculations performed on a series of stereoisomeric methyl 5,7-0-benzylidene-3-deoxy-3-nitro-a-D-heptoseptanosides 28 showed that the lowest energy conformations for these compounds are twist forms derived from and C3,4 chairs this was confirmed by H-NMR spectroscopic data. A study of the hexamethyl ether of scyllo-inositol by H-NMR spectroscopy revealed that all six exocyclic C—O bonds are eclipsed to relieve steric strain... 

---