Inososes synthesis

Other quercitols have been synthesized by catalytic hydrogenolysis of the corresponding inososes (see p. 180). All the known quercitols are shown, with their names, in formulas CXXXIX-CXLIV according to Angyal and Macdonald s proposals,6 the quercitol of acorn is called (+)-profo-quercitol, and natural viburnitol is named (—)-w 6o-quercitol the corresponding Fletcher-Anderson-Lardy names are (+)-1 -deoxy-mwco-inositol and ( —)-1-deoxy-WM/o-inositol. Synthesis of the four as-yet-unknown diastereomers should not present serious difficulties. 

Fukase, H. et al. Synthesis of a Branched-Chain Inosose Derivative, a Versatile Synthon ofN-Substituted Valiolamine Derivatives from D-Glucose. 3.4.2 1992 [58a]... 

The basic permanganate oxidation of conjugated 1,3-dienes is different from those reported for the 1,4-dienes above. Therefore, in the oxidation of cyclopentadiene and 1,3-cyclohexadiene (13) a mixture of five products 14-18 is obtained (equation 4) . In this reaction 14 and 16 are derived from the normal cis hydroxy la tions whereas 17 and 18 were said to be formed from 15 by hydration in what the authors term an epoxidic pathway. Formation of epoxy-diols under similar permanganate oxidations has been found for occidentalol (19), levopimaric acid (20) and a 1-chloro- or 1-bromo-l,3-diene (21) as an intermediate step in the synthesis of (+)-D-c/tfrc-3-inosose and (+)-D-c/r/ro-3-inositol (equation 5). The explanation for the epoxide formation in the oxidation of 1,3-dienes (13, 19-21) is not clear but may be connected to the fact that other additions of permanganate to dienes are possible beyond those commonly observed... 

Fukase, H., and Horii, S., Synthesis of valiolamine and its A-substituted derivatives AO-128, validox-ylamine G, and validamycin G via branched-chain inosose derivatives, J. Org. Chem., 57, 3651, 1992. Morgan, B.P., Holland, D.R., Matthews, B.W., and Bartlett, P.A., Structure-based design of an inhibitor of the zinc peptidase thermolysin, J. Am. Chem. Soc., 116, 3251, 1994. 

This procedure furnishes a practical method for the synthesis of inososes on a small scale. The yield is about 50%, but complete reaction is difficult to effect. The ketones can be isolated through their phenylhydrazones or by column chromatography. 

H. Fukase and S. Horii, Synthesis of a branched-chain inosose derivative. A versatile synthon of JV-substituted valiolamine derivatives from D-glucose, J. Org. Chem., 57 (1992) 3642-3650 3651-3658. 

A range of mono- and di-anhydro-inositols have been prepared from the isomeric 3,6-dibromocyclohexadienemono-epoxides (6) by conventional transformations via the corresponding anhydroconduritols (7). Another paper reports the synthesis of all the 1,2,3,4- and 1,2,4,5-dianhydro-inositols from inositol disulphonates using sodium methoxide. The hydration of three inososes... 

In the interest of devising simple routes to starting materials commonly used in synthesis from sustainable resources, catechol has been made chemo-enzymatically in two steps from glucose in reasonable yield. 2-Deoxy-scyllo-inosose (171) was formed by incubation of D-glucose with recombinant 2-deoxy-scyl/o-inosose synthase and a hexokinase, and this material was reductively dehydrated to catechol by treatment with HI in acetic acid. ... 

Yamauchi N, Kakinuma K. Confirmation of m vitro synthesis of 2 deo y-jcyBo inosose. the earliest intermediate in the biosynthesis of 2-deoxysirepiaminc, using cell free preparations of Streptomyces fradiae. ] Antibiot 1992 45 774-780. 

A mutant strain of Micromonospora purpurea synthesized gentamicin antibiotics on being fed with the inososes (505) and (506), which are presumably converted into streptamine and 2-deoxystreptamine, respectively, prior to incorporation into the intact antibiotics. A mutant strain of S.fradiae synthesized the pseudotrisaccharide ribostamycin (see Vol. 10, p. 131) instead of the pseudotetrasaccharide neomycin. After a second and reverse mutation, new colonies again synthesized neomycin, indicating that ribostamycin may be an intermediate along the biosynthetic pathway leading to neomycin. A chemical synthesis of neomycin C (507) from a derivative of ribostamycin is shown in Scheme 85. ... 

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,... 

Mytilitol (C-methyl-scyllo-mositol) (66) (Fig. 1), m.p. 266-268°, is found in the muscle of Mytilus edvliSy a mussel (67) j and in a marine tunicate, Cionia intestinalis (68), The epimeric isomytilitol obtained synthetically through mi/o-inosose-2 (bioinosose) is 2-C-methyl-m2/o-inositol. Both pentaacetates and hexaacetates can be prepared from mytilitol presumably the tertiary hydroxyl resists acetylation. Postemak (66) has also succeeded in synthesizing hydroxymytilitol, m.p. 247°, and hydroxyiso-mytilitol, m.p. 233°, from m2/o-inosose-2 by means of the Amdt-Eistert synthesis. These are the first-known heptahydric homologs of an inositol. 

The retention times of the pertrimethylsilyl ether derivatives of seventeen disaccharides were determined for two liquid phases, and an attempt was made to relate these to structural features. A quantitative analysis of 2-deoxy-scy//o-inosose by g.c.-m.s. with selected ion monitoring was used to study its enzymatic synthesis, and its m.s. fragmentation was studied using the [2,2- HJ-labelled derivative. ... 

If myo-inosose is an intermediate in the interconversion of these two cychtols by S. griseus it is reasonable to expect that both scy//o-inositol and its 2-keto derivative would stimulate streptomycin production as myo-inositol does. Hunter and Hockenhull (195 5) reported that scy/Zo-inositol when added to S. griseus cultures did not enhance streptomycin production. My(9-inosose-2 partially inhibited production and this inhibition was reversed by administration of scyllo-inositol. On the basis of these findings Hunter (1956) suggested, as one possibility, that myo-inosose inhibits the normal synthesis of streptomycin and that scyZ/o-inositol is required for streptomycin biosynthesis. In another series of experiments (Majumdar and Kutzner, 1962 a) supplementation of culture media with myo-inosose at various concentrations had no detectable effect on strepto-... 

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