- 1L-2,3:4,5-Bis-O-(tetraisopropyldisiloxane-1,3-diyl)-chiro-inositol: a useful intermediate for the preparation of several novel cyclitols
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Keywords: Cyclitols, novel; Inositol, 1L-2,3:4,5-bis-O-(tetraisopropyldisiloxane-1,3-diyl)-chiro-
- Tagliaferri, Frank,Johnson, Stephen C.,Seiple, Todd F.,Baker, David C.
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- Identification and characterization of a novel (?)-vibo-quercitol 1-dehydrogenase from Burkholderia terrae suitable for production of (?)-vibo-quercitol from 2-deoxy-scyllo-inosose
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(?)-vibo-Quercitol is a deoxyinositol (1l-1,2,4/3,5-cyclohexanepentol) that naturally occurs in oak species, honeydew honey, wines aged in oak barrels, and Gymnema sylvestre and is a potential intermediate for pharmaceuticals. We found that (?)-vibo-quercitol is stereoselectively synthesized from 2-deoxy-scyllo-inosose by the reductive reaction of a novel (?)-vibo-quercitol 1-dehydrogenase found in the proteomes of Burkholderia, Pseudomonas, and Arthrobacter. Among them, Burkholderia terrae sp. AKC-020 (40-1) produced a (?)-vibo-quercitol 1-dehydrogenase appropriate for synthesizing (?)-vibo-quercitol with a high diastereomeric excess. The enzyme was strongly induced in Bu. terrae cells when quercitol or 2-deoxy-scyllo-inosose was used as carbon source in the culture medium. The enzyme is NAD(H)-dependent and shows highly specific activity for (?)-vibo-quercitol and myo-inositol among the substrates tested. The enzyme gene (qudh) was obtained by PCR using degenerate primers based on the N-terminal and internal amino acid sequences of the purified enzyme, followed by thermal asymmetric interlaced PCR. The qudh gene showed homology with inositol 2-dehydrogenase (sharing 49.5% amino acid identity with IdhA from Sinorhizobium meliloti 1021). We successfully produced several recombinant (?)-vibo-quercitol 1-dehydrogenases and related enzymes identified by genome database mining using an Escherichia coli expression system. This revealed that scyllo-inositol dehydrogenase (IolX) in Bacillus subtilis can catalyze the reduction of 2-deoxy-scyllo-inosose to yield scyllo-quercitol, a stereoisomer of (?)-vibo-quercitol. Thus, we successfully identified two enzymes to produce both stereoisomers of deoxyinositols that are rare in nature.
- Itoh, Nobuya,Kurokawa, Junji,Toda, Hiroshi,Konishi, Kazunobu
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- Stereoselective syntheses of racemic quercitols and bromoquercitols starting from cyclohexa-1,4-diene: Gala-, epi-, muco-, and neo-quercitol
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The efficient synthesis of gala-, epi-, neo-, and muco-quercitols and some brominated quercitols starting from cyclohexa-1,4-diene is reported. Treatment of the dibromide, obtained by the addition of bromine to cyclohexa-1,4-diene, with m-chloroperbenzoic
- Aydin, G?kay,Savran, Tahir,Akta?, Fatih,Baran, Arif,Balci, Metin
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p. 1511 - 1524
(2013/05/21)
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- Epoxidation of protected (1,4,5)-cyclohex-2-ene-triols and their acid hydrolysis to synthesize quercitols from D-(-)-quinic acid
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Highly stereoselective epoxidations have been achieved in both cyclohexylidene acetal and butane 2,3-bisacetal (BBA) protection of (1,4,5)-cyclohex-2-ene-triols. These epoxy derivatives are all derived from D-(-)-quinic acid and can be used for the synthe
- Shih, Tzenge-Lien,Lin, Ya-Ling
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p. 1809 - 1817
(2007/10/03)
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- An efficient and highly stereoselective synthesis of gala-Quercitol from 1,4-cyclohexadiene
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gala-Quercitol was synthesized from 1,4-cyclohexadiene in seven steps and overall yield of 68%. Reaction of 5,6-dibromo-2,2-dimethylhexahydro-1,3-benzodioxole, synthesized from 1,4-cyclohexadiene in three steps, with excess NaOMe gave (3aα,5α,7aα)-5-metho
- Baran, Arif,Secen, Hasan,Balci, Metin
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p. 1500 - 1502
(2007/10/03)
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- An Advantageous Synthesis of 1D- and 1L-1,2,3,5/4-Cyclohexanepentol
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The title compounds D-10 and L-10 were prepared from 1 in eight steps and in a combined overall yield of 41-49%.
- Biamonte, Marco A.,Vasella, Andrea
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p. 688 - 694
(2007/10/03)
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- A novel synthesis of DL-proto-, and DL-vibo- quercitol via 1,4- cyclohexadiene
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Photooxygenation of 1,4-cyclohexadiene 3 followed by reduction with LiAIH4 or thiourea gave (25/1)-cyclohex-3-ene-triol 7a. trans-Hydroxylation of triol 7a with three different methods afforded both of proto-quercitol 1a and vibo-quercitol 2a.
- Salamci, Emine,Secen, Hasan,Suetbeyaz, Yasar,Balci, Metin
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p. 2223 - 2234
(2007/10/03)
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- A concise and convenient synthesis of DL-proto-quercitol and DL-gala-quercitol via ene reaction of singlet oxygen combined with [2 + 4] cycloaddition to cyclohexadiene
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Photooxygenation of 1,4-cyclohexadiene afforded hydroperoxy endoperoxides 3 and 4 in a ratio of 88:12. Reduction of 3 with LiAlH4 or thiourea followed by acetylation of the hydroxyl group and KMnO4 oxidation of the double bond gave proto-quercitol 10b. Application of the same reaction sequences to 4 resulted in the formation of gala-quercitol 14. Quercitols were easily obtained by ammonolysis of acetate derivatives in MeOH. The outcome of dihydroxylation reactions were supported by conformational analysis.
- Salamci,Secen,Sutbeyaz,Balci
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p. 2453 - 2457
(2007/10/03)
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- Synthesis and evaluation of 3-modified 1D-myo-inositols as inhibitors and substrates of phosphatidylinositol synthase and inhibitors of myo-inositol uptake by cells
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A number of 3-substituted 1D-myo-inositols were synthesized and evaluated as substrates for phosphatidylinositol synthase and uptake by intact cells. 1D-3-Amino-, -3-chloro-, and -3-(acetylthio)-3-deoxy-myo-inositols were all synthesized by nucleophilic d
- Johnson,Dahl,Shih,Schedler,Anderson,Benjamin,Baker
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p. 3628 - 3635
(2007/10/02)
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- A Stereocontrolled Synthesis of proto-Quercitol
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Conduritol A tetramethyl ether (2) has been converted by hydroboration-oxidation into proto-quercitol tetramethyl ether (5) which on demethylation afforded a mixture (2:1) of proto-quercitol (4) and vibo-quercitol (11). proto-Quecitol was also obtained (15percent) from conduritol A tetrabenzoate (3) by a similar sequence.
- Cambie, Richard C.,Renner, Noel D.,Rutledge, Peter S.,Woodgate, Paul D.
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p. 1597 - 1602
(2007/10/02)
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- MICROBIAL OXIDATION IN SYNTHESIS: PREPARATION OF MYO-INOSITOL PHOSPHATES AND RELATED CYCLITOL DERIVATIVES FROM BENZENE.
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Pseudomonas putida oxidation of benzene affords cis-3,5-cyclohexadiene-1,2-diol (2) which is used as a novel precursor for the synthesis of D- and L-myo-inositol 1,4,5-triphosphates, (-)-(1) and (+)-(1).The versatility of this approach to functionalised cyclitols is illustrated in the synthesis of myo-inositol 1-phosphate (19), 6-deoxy, 6-deoxy-6-fluoro, and 6-deoxy-6-methyl myo-inositols (31), (37) and (43), and their 1,4,5-trisphosphate derivatives (33), (39) and (45).
- Ley, Steven V.,Parra, Margarita,Redgrave, Alison J.,Sternfeld, Francine
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p. 4994 - 5026
(2007/10/02)
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- Polyfunctionalised Cyclohexanes from Dianhydrodeoxyinositols. cis-Deoxy-1,3(1,4)-inosadiamines from Benzene
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A ca. 9 : 1 mixture (yield 87 - 90percent) of the stereoisomeric (1α,2α,6α)-/(1α,2β,6α)-2-bromo-7-oxa-bicyclohept-3-enes (7a/8a) is obtained via controlled NBS bromination of 4,5-epoxycyclohexene (5). 7a/8a are quantitatively equilibrated in the presence of tetraalkylammonium bromides (the equilibrium being controlled by the polarity of the solvent (3 : 7 in acetonitrile) and are isolated pure by chromatography.Through selective halogen substitution (7b/8b, 9b - d/10b - d) and ammonolysis the allylic epoxy alcohols 9a/10a are obtained in high yields.Stereospecific epoxidation of 7a/8a yields the (1α,2α,3α,5α,7α)-/(1α,2β,3α,5α,7α)-diepoxy bromides 12a/14a.The latter are equilibrated quantitatively to mixtures favoring either one in the ratio of ca. 9 : 1 (CCl4) and 1 : 9 (CH3CN), respectively.Upon SN2 substitution with ammonium acylates (-> 13b, c/15b, c) and ammonolysis the naturally not occurring dianhydrodeoxyinositols 13a/15a are isolated in practically quantitative yields.The usefulness of 13a/15a and of various derivatives for the stereoselective synthesis of cis-1,4- and cis-1,3-disubstituted cyclohexanetriols is exemplified by reactions with monovalent (H2O, HI, NaN3) and divalent nucleophiles (NH2NH2, CH3NHNH2).I.a. the cis-deoxy-1,3-inosadiamines 1 (2-deoxystreptamine)/2 and the cis-deoxy-1,4-inosadiamines 3/4 become available in high yields.
- Kuehlmeyer, Rainer,Keller, Reinhold,Schwesinger, Reinhard,Netscher, Thomas,Fritz, Hans,Prinzbach, Horst
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p. 1765 - 1800
(2007/10/02)
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- THE PREPARATION OF CYCLOHEXANEPENTOLS FROM INOSITOLS BY DEOXYGENATION
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Several cyclohexapenetols heva been synthesized from inositols by blocking all but one hydroxyl group, converting the free hydroxyl group into its S-methyl dithiocarbonate, and treating it with tributylstannane.Suitable blocking-groups are methyl, benzyl, and methylthiomethyl ethers, and acetals.One cyclohexanepentol was prepared by the reductive deamination of an aminodeoxyinositol.
- Angyal, Stephen J.,Odier, Leon
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p. 209 - 220
(2007/10/02)
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