- A short, stereoselective synthesis of neo-inositol
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A practical synthesis of neo-inositol is described in which the target is prepared on a multigram scale in six operations from bromobenzene. Copyright (C) 2000 Elsevier Science Ltd.
- Hudlicky, Tomas,Restrepo-Sanchez, Nora,Kary, Pierre D.,Jaramillo-Gomez, Luz M.
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- METHODS OF SYNTHESIS OF SCYLLITOL AND RELATED COMPOUNDS
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Methods of synthesis of scyllitol diborate and related compounds are provided, including methods that are performed in all-aqueous solutions. Also provided are methods in which the reaction products are recycled to increase the efficiency of the process. The methods include the steps of conversion of a solution of inositol to scyllitol, conversion of scyllitol in the solution to scyllitol diborate, and isolation of the scyllitol diborate from the solution. The scyllitol diborate is reacted to form substantially pure scyllitol diborate, and the remaining solution is efficiently recycled to scyllitol diborate, then to additional substantially pure scyllitol. This scyllitol diborate recycling step can be applied to a variety of processes to improve the yield of scyllitol. The methods are highly efficient and result in large scale reaction products of high purity.
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Page/Page column 58-61
(2012/05/04)
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- A short and efficient route from myo - To neo -inositol
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An efficient route from myo- to neo-inositol is described. The key steps of the sequence are oxidation of the hydroxy group at C-5 to the corresponding ketone, followed by a highly (dr = 7.8:1) stereoselective reduction. The route includes nine steps with an overall yield of 51% and is therefore superior to all hitherto reported methods for the preparation of neo-inositol. Georg Thieme Verlag Stuttgart New York.
- Wessig, Pablo,M?llnitz, Kristian,Hübner, Sebastian
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scheme or table
p. 1497 - 1500
(2010/09/05)
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- Common-intermediate strategy for synthesis of conduritols and inositols via beta-hydroxy cyclohexenylsilanes.
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[reaction: see text] Syntheses of conduritols B-D and F and d-(+)-chiro- and neo-inositols from cyclohexenylsilane intermediates are described. The key cyclohexylsilane intermediates 5 and 14 were synthesized by stereoselective olefin dihydroxylation of t
- Heo, Jung-Nyoung,Holson, Edward B,Roush, William R
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p. 1697 - 1700
(2007/10/03)
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- Stereoselective synthesis of myo-, neo-, L-chiro, D-chiro, allo-, scyllo-, and epi-inositol systems via conduritols prepared from p-benzoquinone
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A practical route is described for the flexible preparation of a wide variety of inositol stereoisomers and their polyphosphates. The potential of this approach is demonstrated by the synthesis of myo-, L-chiro-, D-chiro-, epi-, scyllo-, allo-, and neo-inositol systems. Optically pure compounds in either enantiomeric form can be prepared from p-benzoquinone via enzymatic resolution of a derived conduritol B key intermediate. High-performance anion-exchange chromatography with pulsed amperometric detection permits inositol stereoisomers to be resolved and detected with high sensitivity. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003.
- Podeschwa, Michael,Plettenburg, Oliver,Vom Brocke, Jochen,Block, Oliver,Adelt, Stephan,Altenbach, Hans-Josef
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p. 1958 - 1972
(2007/10/03)
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- Stereo- and regiospecificity of yeast phytases-chemical synthesis and enzymatic conversion of the substrate analogues neo- and L-chiro-inositol hexakisphosphate
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Phytases are enzymes that catalyze the hydrolysis of phosphate esters in myo-inositol hexakisphosphate (phytic acid). The precise routes of enzymatic dephosphorylation by phytases of the yeast strains Saccharomyces cerevisiae and Pichia rhodanensis have been investigated up to the myo-inositol trisphosphate level, including the absolute configuration of the intermediates. Stereoselective assignment of the myo-inositol pentakisphosphates (D-myo-inositol 1,2,4,5,6-pentakisphosphate and D-myo-inositol 1,2,3,4,5-pentakisphosphate) generated was accomplished by a new method based on enantiospecific enzymatic conversion and HPLC analysis. Via conduritol B or E derivatives the total syntheses of two epimers of myo-inositol hexakisphosphate, neo-inositol hexakisphosphate and L-chiro-inositol hexakisphosphate were performed to examine the specificity of the yeast phytases with these substrate analogues. A comparison of kinetic data and the degradation pathways determined gave the first hints about the molecular recognition of inositol hexakisphosphates by the enzymes. Exploitation of the high stereo- and regiospecificity observed in the dephosphorylation of neo- and L-chiro-inositol hexakisphosphate made it possible to establish enzyme-assisted steps for the synthesis of D-neo-inositol 1,2,5,6-tetrakisphosphate, L-chiro-inositol 1,2,3,5,6-pentakisphosphate and L-chiro-inositol 1,2,3,6-tetrakisphosphate.
- Adelt, Stephan,Podeschwa, Michael,Dallmann, Guido,Altenbach, Hans-Josef,Vogel, Guenter
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- Synthesis of D-chiro-3-inosose and (+)-D-chiro-inositol
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There are described novel biocatalytic and chemical processes for the synthesis of various oxygenated compounds. Particularly, there are described processes for the synthesis of a useful synthon (12) made by reacting a protected diol (acetonide) with permanganate under appropriate conditions. Such synthon is useful of the synthesis of various pharmaceutically important compounds such as D-chiro-inositol and D-chiro-3-inosose. Also, there are disclosed novel compounds, including specifically the synthon (12) and compounds derived therefrom.
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- Novel synthesis of enantiomerically pure natural inositols and their diastereoisomers
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The various inositol polyphosphates have been found to trigger many important biological processes. Although the knowledge of this phosphoinositide signaling system has been discovered in the past 10 years, many factors remain unclear. For this reason, there is an increased demand for supplies of D-myo-inositol and particularly of novel analogues to investigate these biological mechanisms in more detail. Herein, we report the efficient syntheses of all diastereoisomers of inositol starting with 6-O-acetyl-5-enopyranosides. Conversion of 6-O-acetyl-5-enopyranosides into the corresponding substituted cyclohexanones (Ferrier-II rearrangement) was found to proceed efficiently with a catalytic amount of palladium dichloride. Stereoselective reduction of β-hydroxy ketones obtained provided the precursors to all inositol diastereoisomers in good to excellent yields and with high stereoselectivities. Good accessibility of these enantiomerically pure inositol diastereoisomers results in the efficient syntheses of D-myo-inositol 1,4,5-trisphosphate and D-myo-inositol 1,3,4,5-tetrakisphosphate.
- Takahashi,Kittaka,Ikegami
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p. 2705 - 2716
(2007/10/03)
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- A concise synthesis of neo-inositol
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neo-Inositol was prepared on a multigram scale in five steps from myo-inositol without recourse to column chromatography. The synthesis includes a large-scale preparation of 1,6:3,4-bis-[O-(2,3-dimethoxybutane-2,3-diyl)]-myo-inositol and a high-yielding i
- Riley, Andrew M.,Jenkins, David J.,Potter, Barry V.L.
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p. 277 - 281
(2007/10/03)
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- Transformation of cyclohexene to enantiopure cyclitols mediated by sequential oxyselenenylation with (S,S)-hydrobenzoin: Synthesis of D-chiro-inositol and muco-quercitol
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Oxyselenenylation of cyclohexene with (S,S)-hydrobenzoin and subsequent oxidation-elimination allows isolation of an allylic ether in which further phenylselenenylation is completely regioselective, thus allowing entry to the cyclitols D-chiro-inositol and muco-quercitol.
- Kim, Kwan Soo,Park, Jong H.,Moon, Hoi Kyung,Yi, Hann
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p. 1945 - 1946
(2007/10/03)
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- Microbial Oxidation of Aromatics in Enantiocontrolled Synthesis. Part 1.Expedient and General Asymmetric Synthesis of Inositols and Carbohydrates via and Unusual Oxidation of a Polarized Diene with Potassium Permanganate
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This paper reports on the details of a general design of carbohydrates and cyclitols from biocatalytically derived synthons.Homochiral 1-halogenocyclohexa-4,6-diene-2,3-diols 1a and 1b have been generated from chloro- and bromobenzene, respectively, by means of bacterial dioxygenase of Pseudomonas putida 39D.These chiral synthons have been manipulated to cyclitols and carbohydrates by further stereoselective functionalizations.The preperation of D-chiro-inositol, neo-inositol, muco-inositol, and allo-inositol exemplifies their use in enantiocontrolled synthesis.A novel oxidation of polarized dienes with KMnO4 resulted in the synthesis of α-halogeno epoxy diols, which proved unexpectedly stable.A mechanism is proposed for this transformation and placed in context with the only four reported examples of this reaction in the literature.In addition to the application of this new chemistry to the synthesis of cyclitols, chloro epoxy diol 21a has been transformed into a series of cyclitol synthons by reductive or hydrolytic operations.Reaction of 21a with ammonia led to the preparation of highly oxygenated pyrazines, whose structure were proven by X-ray crystallography.The use of 21a in the preparation of D-chiro-3-inosose, a hitherto unreported cyclitol derivative, is also reported.In addition, chloro epoxy diol 21a was transformed into D-erythruronolactone, completing the synthesis of this important chiral pool reagent in two operations from chlorobenzene.Oxidative cleavage of tetrol 20 yielded D-mannosolactone identical with an authentic sample.
- Hudlicky, Tomas,Mandel, Martin,Rouden, Jacques,Lee, Robert S.,Bachmann, Bryan,et al.
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p. 1553 - 1568
(2007/10/02)
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- General Synthesis of Inositols by Hydrolysis of Conduritol Epoxides Obtained Biocatalytically from Halogenobenzenes: (+)-D-chiro-Inositol, allo-Inositol, muco-Inositol and neo-Inositol
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Four of the nine isomeric inositols have been prepared by hydrolytic opening of epoxides derived from 3-halogenocyclohexa-3,5-diene-1,2-diol by further oxidation with potassium permanganate or by reduction of chiro-3-inosose (2L-2,3,6/4,5-pentahydroxycyclohexanone).
- Mandel, Martin,Hudlicky, Thomas
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p. 741 - 744
(2007/10/02)
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- GLYCOSYL-INOSITOL DERIVATIVES III. SYNTHESIS OF HEXOSAMINE-INOSITOL-PHOSPHATES RELATED TO PUTATIVE INSULIN MEDIATORS
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The disaccharides related to glycosyl phosphatidyl inositol anchors of membrane proteins, 4-O-(2-amino-2-deoxy-α-D-glucopyranosyl)-D-myo-inositol-1-phosphate and 4-O-(2-amino-2-deoxy-α-D-galactopyranosyl)-D-chiro-inositol-1-phosphate, have been prepared from optically resolved myo-inositol derivatives.The chiro-inositol moiety was obtained by epimerization of a selectively blocked myo-inositol-triflate ester.The resolved inositols were subsequently phosphorylated to yield the disaccharide aglycones.The amino-sugar components were prepared by azidonitration of suitably protected glucal and galactal derivatives.The derived pyranosyl chlorides were then condensed with the inositol phosphates using silver triflate as the promoter.
- Berlin, William K.,Zhang, Wen-Sheng,Shen, T. Y.
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- NOVEL BIOSYNTHESIS OF D-PINITOL IN SIMMONDSIA CHINENSIS
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Chase experiments with 14CO2 and feeding experiments with labwelled inositols showed that D-pinitol in leaves of Simmondsia chinensis arises via epimerization of D-ononitol.This finding represents an alternative pathway, since D-pinitol is formed in gymnosperms and other plants by epimerization of sequoyitol.Key Word Index -- Simmondsia chinensis; Simmondsiaceae; jojoba; biosynthesis; cyclitols; D-pinitol; D-ononitol.
- Dittrich, Peter,Korak, Andrea
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- Polyfunctionalised Cyclohexanes from Dianhydroinositols. cis-1,3(1,4)-Inosadiamines from Benzene
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The preparative value of the dianhydroinositols 4 - 6, which are readily available from benzene, for the total synthesis of cis-1,4- and cis-1,3-disubstituted cyclohexanetetrols is demonstrated.With monovalent reagents (H2O, HI, NaN3, NH2NH2) the twofold epoxide opening proceeds regioselectively (1,4-disubstitution) yielding the muco- and chiro-cyclohexane derivatives 9, 17, and 26.With hydrazine and N,N'-dimethylhydrazine as 1,2-dinucleophiles the cis-1,3-inosadiamines 7 g (5-epistreptamine) and 16 g, j (2-epistreptamine, actinamine) are obtained from 4/5 in good yields (75 - 90percent).From the less symmetrical 6, however, only the mixture of 25 g (streptamine) and 27 g is produced in modest yield (ca. 50percent).The epoxide opening reactions starting from 4 - 6 are kinetically so similar that a selective opening is not possible.
- Schubert, Juergen,Keller, Reinhold,Schwesinger, Reinhard,Prinzbach, Horst
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p. 2524 - 2545
(2007/10/02)
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- PURIFICATION AND STRUCTURE DETERMINATION OF THREE α-D-GALACTOPYRANOSYLCYCLITOLS FROM SOYA BEAN
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Three α-D-galactopyranosylcyclitols previously isolated from soya bean are shown to be 1D-2-O-(α-D-galactopyranosyl)-4-O-methyl-chiro-inositol, 1D-5-O-(α-D-galactopyranosyl)-4-O-methyl-chiro-inositol, and 1D-2-O-(α-D-galactopyranosyl)-chiro-inositol.Assignments of the (13)C-n.m.r. spectra of these compounds and of 1L-1-O-(α-D-galactopyranosyl)-myo-inositol (galactinol) are presented.The mass spectra of derivatives prepared by permethylation or perdeuteriomethylation, followed by hydrolysis and acetylation or methylation are discussed.
- Schweizer, Thomas F.,Horman, Ian
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