Synthesis from inositols

7 Synthesis from inositols Syntheses of 1 and 2 as well as the L-analogues starting from the seven-membered lactones 146 and 152, prepared from myo-inositol, have been 

Likewise, (—)-nojirimycin (154) and (—)-l-deoxynojiriniycin (155) were prepared starting from the lactone 152. 

Matsumura, S. Biomoto, H. Aoyagj, Y. Yoshikuni, Y Yagi, M. Japanese Patent Application 78/99,208, Aug. 14, 1978 Chem. Abstr. 93 (1980) 66581s Japanese Kokai Tokkyo Koho 8027,136, 1980 Japanese Patent Kokoku 59,27338,1984. 

Inouye, S. Tsuraoka, T. Koaze, Y Niida, T. Agric. Biol. Chem. 34 (1970) 966. 

Aoyagi, Y Murai, H. Nippon KagakuKaishi50 (1976) 571 Chem. Abstr. 86 (1977) 167851r. 

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Sasaki, K., and Taylor, I.E.P., 1986, myo-Inositol synthesis from [l-3H]glucose in Phaseolus vulgaris L. during early stages of germination. Plant Physiol. 81 493—496. 

Walker, J.B., 1995, Enzymatic synthesis of aminocyclitol moieties of aminoglycoside antibiotics from inositol by Streptomyces spp. Detection of glutamine-aminocyclitol aminotransferase and diaminocyclitol aminotransferase activities in a spectinomycin producer. J. Bacteriol. 177 818-822. 

A number of tetraphosphate analogues, e.g. 24, have been prepared with a view to increasing cell membrane permeation properties. Routes to 3,4,5,6-tetrakis-phosphates, e.g. 25, of DL-l,2-dideoxy-l,2-difluoro-mjo-inositol and dl-1,2-dideoxy-1,2-difluoro-5cj//o-inositol have been reported.The fluoro substituents were introduced using DAST to displace hydroxy groups. However, the difluorina-tion could not be achieved in one step due to competing formation of a 1,4-anhydro derivative. The synthesis, from wjo-inositol monobenzoate derivatives, of all four... 

Par, Y., Hong, Y., Kim, S., Piccariello, T, Farese, R.V., and Larner, J. In vivo chiro-inositol metabohsm in the rat a defect in chiro-inositol synthesis from myoinositol and an increased incorporation of chiro-[ H]inositol into phospholipid in the Goto-Kakizaki (GK) rat. Mol. Cells, 1998, 8, 301-309. 

Synthesis from myo-inositol Total syntheses of trehazolin (1) and its isomers have established both its structure and absolute configuration (Schemes 11-13). Thus, base-catalyzed nitromethane condensation of the dialdehyde generated by periodate oxidation of ( )-l,2-(9-cyclohexylidene-myo-inositol (74) gave a mixture of the nitro-diols, which was hydrogenated in the presence of Raney nickel, followed by acetylation to afford the three diastereoisomeric 2,3-(9-cyclohexylidene derivatives 75 (40%), ( )-76 (5%) and 77 (5%) of 5-acetamido-l,4-0-acetylcyclopentane-l,2,3,4-tetraol. The minor racemic mixture 76 was de-O-acetylated, N,0-isopropylidenated, and then resolved by... 

Three potential sources for cellular inositol are diet, de novo biosynthesis, and recycling of inositol. Inositol is biosynthesized from glucose in the brain and testes, and other tissues to a lesser extent. The rate-limiting step in the inositol biosynthetic pathway appears to be the synthesis of inositol-3-phosphate from glucose-6-phosphate (C.P. Downes,... 

To achieve total synthesis of inositol phosphates and related derivatives, multiple phosphorylation of polyol derivatives is the most crucial step. Use of dianilinophosphoric chloride 8 was the only method of choice for this purpose. However, its reactivity is not satisfactory for perphosphorylation of inositols and furthermore spontaneous deprotection of several dianilinophosphoric esters in the same molecules is quite difficult, while phosphorylation of D-2,3,6-tribenzyl-myo-inositol 9 with the chloride 8 giving 11 in 60% yield was accomplished after exploring proper reaction conditions in the first total synthesis of Ins(l,4,5)P3 (Scheme 2-1).However, the phosphorylation product 12 was not formed at all from 10, a positional isomer of 9 under similar conditions. In 1987, it was reported that the reaction of tetrabenzyl pyrophosphate (TBPP, 13) with alkoxides generated in situ by the action of a strong base such as NaH.l c KH, - or butyllithium b on inositols smoothly gave the desired polyphosphorylated products in good yields. Examples are shown in Scheme 2-1. 

J. R. Falck and A. Abdali, in A. B. Reitz (Ed), ACS Symposium Series 463, Inositol Phosphates and Derivatives, Synthesis, Biochemistry, and Therapeutic Potential. Chapter 11 Enantiospecific Synthesis of Inositol Polyphosphates, Phosphatidylinositid.es, and Analogues from (-)-Quinic Acid, American Chemical Society, Washington, D.C., 1991, pp 145-154. 

Petersen Wakui, 1990 Tsien Tsien, 1990 Meyer Stryer, 1991 Tsunoda, 1991). These oscillations are also observed in several egg species after fertilization (Cuthbertson Cobbold, 1985 Miyazaki et al, 1986 Miyazaki, 1988). It appears that the external stimulus elicits the synthesis of inositol 1,4,5-trisphosphate (IP3), the intracellular messenger that triggers the release of Ca from an intracellular pool sensitive to IP3. This increase in cytosolic Cdi in turn elicits the release of Cd from a second pool, insensitive to IP3 (Berridge Irvine, 1989 Berridge, 1993). 

Synthesis of Inosamine and Inosadiamine Derivatives from Inositol Bromohydrins, M. L. Wolfrom, Jack Radell, R. M. Husband, and G. E. McCasland,/. Amer. Chem. Soc., 79, 160-164 (1957). 

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... 

Reviews have appeared on the synthesis of inositols, carba sugars, conduritols and amino conduritols utilizing the non-carbohydrate sources of benzene cis-diols, quinic acid and Vogel s naked sugar methodology. Other reviews on the preparation of cyclophellitol and ep/-cyclophellitol from glycals and the use of D-glyceraldehyde as a chiral precursor in Diels-Alder and 1,3-dipolar cycloaddition approaches to carbocyclic derivatives have also been reported. 

The Ferrier carbocyclization reaction of an enol-acetate substrate gives an a,p-dihydroxy-cyclohexanol derivative (see Schemes 12.7 and 12.81. This transformation would be effective for the chiral synthesis of inositol derivatives. A retrosynthetic plan for the marine natural product tetrodotoxin 88 based on the enol-acetate version of Ferrier carbocyclization is shown in Scheme 12.22. Tetrodotoxin 88 was planned to be synthesized from lactone 89, the precursor of which would be highly functionalized cyclohexane 90. Cyclohexane 90 was envisioned to arise from cyclohexanone 91. For the preparation of 91, Ferrier carbocyclization of enol acetate 92 would be a suitable transformation. d-Glucose derivative 93 possessing an exo-methylene at C-3 would serve as a promising precursor of 92. 

Because of the widespread occurrence of m /o-inositol in animals, plants, yeasts, molds, and bacteria, many attempts have been made at its synthesis. The chemical syntheses have been considered earlier in this chapter. Biochemical synthesis of inositol from n-glucose or D-glucose phosphate by action of a plant cyclase has been reported 126). The evidence for this transformation is a positive Scherer test there has been no definitive evidence in the form of isolation of myo-inositol. Evidence for synthesis in the animal body is based on the isolation of C Mabeled myo-inositol after the administration of C -labeled n-glucose 32h). 

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