- Prebiotic synthesis of 2-deoxy-d-ribose from interstellar building blocks promoted by amino esters or amino nitriles
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Understanding the prebiotic genesis of 2-deoxy-d-ribose, which forms the backbone of DNA, is of crucial importance to unravelling the origins of life, yet remains open to debate. Here we demonstrate that 20 mol% of proteinogenic amino esters promote the selective formation of 2-deoxy-d-ribose over 2-deoxy-d-threopentose in combined yields of ≥4%. We also demonstrate the first aldol reaction promoted by prebiotically-relevant proteinogenic amino nitriles (20 mol%) for the enantioselective synthesis of d-glyceraldehyde with 6% ee, and its subsequent conversion into 2-deoxy-d-ribose in yields of ≥ 5%. Finally, we explore the combination of these two steps in a one-pot process using 20 mol% of an amino ester or amino nitrile promoter. It is hence demonstrated that three interstellar starting materials, when mixed together with an appropriate promoter, can directly lead to the formation of a mixture of higher carbohydrates, including 2-deoxy-d-ribose.
- Steer, Andrew M.,Bia, Nicolas,Smith, David K.,Clarke, Paul A.
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supporting information
p. 10362 - 10365
(2017/09/25)
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- Method for preparing 2-deoxy-D-ribose
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The invention provides a method for preparing 2-deoxy-D-ribose, and belongs to the technical field of organic synthesis.The method includes the following steps that A, 3,4-O-diacetyl-D-arabinal is dissolved into organic solvents, lithium bromide or lithium chloride, strong acid cation exchange resin and water are added, and the mixture is reacted to obtain 3,4-O-diacetyl-deoxy-D-ribose; B, the 3,4-O-diacetyl-deoxy-D-ribose is subjected to hydrolysis reaction to obtain the 2-deoxy-D-ribose.According to the method for preparing the 2-deoxy-D-ribose, due to the effect of the lithium bromide, the strong acid cation exchange resin and the water, the yield of the 2-deoxy-D-ribose is increased, postprocessing is simple and convenient, production cost is reduced, and therefore the method can be widely applied to industrial production.
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- Biosynthesis of anti-HCV compounds using thermophilic microorganisms
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This work describes the application of thermophilic microorganisms for obtaining 6-halogenated purine nucleosides. Biosynthesis of 6-chloropurine- 2′-deoxyriboside and 6-chloropurine riboside was achieved by Geobacillus stearothermophilus CECT 43 with a conversion of 90% and 68%, respectively. Furthermore, the selected microorganism was satisfactorily stabilized by immobilization in an agarose matrix. This biocatalyst can be reused at least 70 times without significant loss of activity, obtaining 379 mg/L of 6-chloropurine-2′-deoxyriboside. The obtained compounds can be used as antiviral agents.
- Rivero, Cintia W.,De Benedetti, Eliana C.,Sambeth, Jorge E.,Lozano, Mario E.,Trelles, Jorge A.
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p. 6059 - 6062
(2012/10/29)
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- The 1H NMR method for the determination of the absolute configuration of 1,2,3-prim,sec,sec-triols
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The absolute configuration of 1,2,3-prim,sec,sec-triols can be assigned by comparison of the 1H NMR spectra of the tris-(R)- and the tris-(S)-MPA ester derivatives. An experimental demonstration of this correlation with 24 triols of known absolute configuration and a protocol using two parameters-ΔδRS(H3) and the difference between ΔδRS(H2) and ΔδRS(H3) = |Δ(ΔδRS)|-for its application to the determination of the absolute configuration of other triols are presented.
- Lallana, Enrique,Freire, Felix,Seco, Jose Manuel,Quinoa, Emilio,Riguera, Ricardo
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p. 4449 - 4452
(2007/10/03)
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- PROCESS FOR PRODUCING 2-DEOXYALDOSE COMPOUND
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An object of the present invention is to provide a method for preparing 2-deoxyaldoses on industrial scale in which the yield or the volumetric efficiency is excellent and the operation is simple, as compared to the conventionally known preparation method.A compound represented by the general formula (1) such as 2-keto-3-deoxygluconic acid or the like is reduced by the catalytic hydrogenation method using a metal such as palladium or the like, or a compound represented by the general formula (1) such as 2-keto-3-deoxygluconic acid or the like is reduced by using a hydride reducing agent in a solvent of not more than 30 weight times the amount of the above compound, for synthesizing 2-keto-3-deoxyaldonic acid. The 2-keto-deoxyaldonic acid was decarboxylated to obtain 2-deoxyaldoses.The method of the present invention is economical and efficiently excellent.
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Page/Page column 11
(2008/06/13)
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- Novel gluconate dehydratase
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A novel gluconate dehydratase derived from Achromobacter xylosoxidans and a gene encoding the gluconate dehydratase are provided. By reacting the gluconate dehydratase or a transformed cell containing the gene with an aldonic acid, the corresponding 2-keto-3-deoxyaldonic acid can be efficiently produced.
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- Production of aldoses
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An aldose having n-1 carbon atoms is produced from an aldonic acid having n carbon atoms using hypochlorous acid or a hypochlorite in a high yield at low cost with safety, by treating the reaction mixture with a compound having reactivity with the hypochlorous acid or hypochlorite higher than that with the produced aldose.
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- Intermediates for preparing optically active carboxylic acids
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A process is described for preparing optically active alpha-arylalkanoic acids consisting of rearranging an optically active ketal of formula STR1 in which the substituents have the meaning given in the description of the invention.
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- SUBSTRATE SPECIFICITY AND ENANTIOSELECTIVITY OF PENICILLINACYLASE CATALYZED HYDROLYSIS OF PHENACETYL ESTERS OF SYNTHETICALLY USEFUL CARBINOLS
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Penicillinacylase from E. coli, immobilized on Eupergit C beads catalyzes the hydrolysis in water/CH3CN 10:1, at pH 7.5 and 23 deg C, of a set of O-phenylacetate esters of primary carbinols.The highest enantioselectivity is observed in the case of the 2,2-dimethyl-1,3-dioxolane-4-methanols structurally related to the penicillin (1) framework.Minor modifications of this basic structure are not altering the acceptability by the enzyme, but significantly decrease the enantioselectivity of the hydrolysis, as does the use of benzene as solvent and Sepharose-bound enzyme.
- Fuganti, Claudio,Grasselli, Piero,Servi, Stefano,Lazzarini, Ameriga,Casati, Paolo
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p. 2575 - 2582
(2007/10/02)
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- Fumarase-Catalyzed Synthesis of L-threo-Chloromalic Acid and Its Conversion to 2-Deoxy-D-ribose and D-erythro-Sphingosine
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This paper describes the use of pig heart fumarase (E.C. 4.2.1.2) as a catalyst in the multigram synthesis of L-threo-chloromalic acid (1) (>99.5percent enantiomeric excess) on 50-g scale.L-threo-Fluoromalic acid has been synthesized in a coupled enzymic system from difluorofumaric acid.Compound 1 serves as starting material for syntheses of 2-deoxy-D-ribose and D-erythro-sphingosine.
- Findeis, Mark A.,Whitesides, George M.
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p. 2838 - 2848
(2007/10/02)
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- Ring-chain Tautomerism of 2-Deoxy-D-ribose: Complete Analysis of the Dynamics by NMR Line-shape Simulation and Spin-saturation Transfer
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For the first time all rate constants assoziated with the pyranose-aldehyde-furanose equilibrium of a sugar (2-deoxy-D-ribose) have been determined by NMR.Line-shape analysis and spin-saturation transfer give the same results.
- Bauer, Hans,Brinkmeier, Arno,Buddrus, Joachim,Jablonowski, Maria
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p. 1804 - 1808
(2007/10/02)
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- Radiation-Induced Degradation of Purine and Pyrimidine 2'-Deoxyribonucleosides in Aqueous KBr Solutions
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Steady-state γ-radiolysis of 5E-4 M pyrimidine and purine 2'-deoxyribonucleosides in aqueous solutions saturated with N2, N2O and O2, respectively, have been carried out in the presence of 0.1 M KBr.The main final degradation products have been isolated and characterised by various spectroscopic measurements including 1H and 13C NMR, UV, C.D. and mass spectrometry.The radiation-induced decomposition of thymidine is mostly accounted for by an ionic mechanism involving Br2, the decay product of Br2, as the reactive oxidising specie.On the other hand the degradation of the purine ring of 2'-deoxyadenosine and 2'-deoxyguanosine may be accounted for by the action of Br2 or Br3. - Keywords: 2'-Deoxyribonucleosides, Inorganic Radical, γ-Irradiation, Radical Reactions, Thymidine Oxidation
- Cadet, J.,Voituriez, L.,Berger, M.,Myers, L. S., (Jr.)
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p. 1643 - 1651
(2007/10/02)
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- A kinetic and nuclear magnetic resonance study of methylated pyrimidine nucleosides
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Alkylated pyrimidine nucleosides are of interest from the viewpoint of mutagenesis and carcinogenesis. (1)H and (13)C nmr data are presented for a series of 2'-deoxynucleosides methylated at the O2-, O4-, and N3-positions of the base, and discussed in terms of their physical properties.The pH dependence of the stability of the O2- and O4-methylated 2'-deoxyribosides as well as the corresponding ribosides was examined by (1)H nmr and ultraviolet (uv) spectrophotometric methods.
- Allore, B. D.,Queen, A.,Blonski, W. J.,Hruska, F. E.
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p. 2397 - 2402
(2007/10/02)
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- Acyclic Stereoselection. 12. Double Stereodifferentiation with Mutual Kinetic Resolution. A Superior Class of Reagents for Control of Cram's Rule Stereoselection in Synthesis of erythro-α-Alkyl-β-hydroxy Carboxylic Acids from Chiral Aldehydes
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Chiral α- ketones 7-9 have been prepared and their aldol condesations studied.Compound 8 shows from good to excellent inherent diastereoface selectivity in reactions with achiral aldehydes.Stereoselectivity is related to the size of the alkyl group attached to the aldehyde carbonyl; highest selectivity is observed with diphenylacetaldehyde (>10:1) and pivaldehyde (>19:1).Ketone 8 also shows high diastereoface selectivity in its reactions with chiral, racemic aldehydes 21, 25, 29, and 17, only one stereoisomeric aldol being obtained in each case.Furthermore, the four aforementioned aldehydes show much higher diastereoface selectivity with ketone 8 than they do with the related ketone 1.As a result, the reactions of racemic 8 with these chiral, racemic aldehydes show a high degree of "mutual kinetic resolution".In fact, the rate of the (R)-enolate plus (R)-aldehyde condensation is at least 35 times the rate of the (R)-enolate plus (S)-aldehyde condensation.It is shown by simple logical argument that such mutual kinetic resolution is expected in reactions between two chiral racemic compounds and that the magnitude of the effect should be proportional to the inherent diastereoselectivity shown by each compound in its reaction with achiral reaction partners.Thus, reagents such as 8 can be used to obtain the benefits of double stereodifferentiation even in the racemic form.As an application of the chemistry developed, (+/-)-blastmycinone (47) has been prepared in four steps from ketone 9 (20percent overall yield).
- Heathcock, Clayton H.,Pirrung, Michael C.,Lampe, John,Buse, Charles T.,Young, Steven D.
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p. 2290 - 2300
(2007/10/02)
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- Acyclic Stereoselection. 9. Stereochemistry of the Addition of Lithium Enolates to α-Alkoxy Aldehydes
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The stereochemistry of addition of lithium enolates derived from esters and ketones to the α-alkoxy aldehydes 1-5 has been investigated.In all cases, the predominant product is that predicted by application of Felkin's model for asymmetric induction and by assuming the alkoxy group to be the "large" group.The Cram cyclic model for asymmetric induction is not followed.Stereostructures have been assigned by a combination of conversion to products of known stereostructure, 13C and 1H NMR correlations, and single-crystal X-ray analysis.
- Heathcock, Clayton H.,Young, Steven D.,Hagen, James P.,Pirrung, Michael C.,White, Charles T.,VanDerveer, Don
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p. 3846 - 3856
(2007/10/02)
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