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1.
A simple method for the preparation of fully protected 2′-deoxynucleoside-3′-phosphates is described. The main step, phosphorylation of partially protected deoxynucleosides, is performed with the monofunctional reagent p-chlorophenyl (2-cyanoethyl) phosphochloridate3) ( 2 ) in dioxane. This reagent is quickly prepared from readily accessible p-chlorophenyl phosphodichloridate by reaction with 3-hydroxypropionitrile and triethylamine in dioxane or ether. The crude reagent is used directly for phosphorylation. After chromatography, protected deoxynucleoside-3′-phosphates were isolated in yields of 80–87%. The method described here, which has been optimized in detail, represents a simple alternative to published methods. 相似文献
2.
Ayhan S. Demir Ömer Reis Ilker Esiringü Barbaros Reis Sehriban Baris 《Tetrahedron》2007,63(1):160-165
Acylphosphonates, which are easily available from carboxylic acids, are potent acyl anion precursors and undergo cyanide ion promoted phosphonate-phosphate rearrangement to provide the corresponding acyl anion equivalents as reactive intermediates. The protonation of these acyl anion equivalents furnished cyanohydrin O-phosphates in good yields. For the high yield formation of cyanohydrin O-phosphates from arylphosphonates THF should be used and from alkylphosphonates DME was used. 相似文献
3.
Four nucleoside diphosphate 6-deoxy-l-sugars have been efficiently synthesized by coupling sugar-1-phosphates prepared from the H-phosphonate precursors with nucleoside 5′-phosphoropiperidates in the presence of 4,5-dicyanoimidazole (DCI) as the activator. Compared to the conventional 1H-tetrazole-promoted phosphoromorpholidate method, the new phosphoropiperidate/DCI system significantly shortened the reaction time and afforded nucleoside diphosphate sugars in excellent isolated yields. 相似文献
4.
β-d-Glucopyronosylphosphates were obtained in high yields from 0-α-d-glucopyranosyl trichloroacetimidates – and phosphoric acid monoesters and diesters –. Some β-phosphates were transformed into the corresponding α-derivatives by acid catalysis. 相似文献
5.
W. T. Markiewicz T. K. Wyrzykiewicz 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1-4)
Abstract Oligonucleotides bearing 3′-phosphates groups are required for studying chemical ligation (1), thermodynamic and spectroscopic analyses (2). Synthetic methods for oligodeoxynucleotides with terminal 3′-phosphates were already established either in solution (3) or on solid supports (4,5). In this communication we describe the preparation of glass supports with degradable linkers I which allow an easy access to 3′-phosphorylated oligonucleotides by a phosphoroamidite method. 相似文献
6.
[reaction: see text] Direct synthetic access to glycosyl-1-phosphates is accomplished with the dehydrative coupling of carbohydrate hemiacetals and dialkyl phosphates, employing dibenzothiophene-5-oxide and triflic anhydride. The procedure offers a new and versatile method for efficient preparation of a host of glycosyl-1-phosphates of variable structure with good control over anomeric selectivity. 相似文献
7.
Timmons SC Hui JP Pearson JL Peltier P Daniellou R Nugier-Chauvin C Soo EC Syvitski RT Ferrières V Jakeman DL 《Organic letters》2008,10(2):161-163
A bacterial alpha-d-glucopyranosyl-1-phosphate thymidylyltransferase was found to couple four hexofuranosyl-1-phosphates, as well as a pentofuranosyl-1-phosphate, with deoxythymidine 5'-triphosphate, providing access to furanosyl nucleotides. The enzymatic reaction mixtures were analyzed by electrospray ionization mass spectrometry and NMR spectroscopy to determine the anomeric stereochemistry of furanosyl nucleotide products. This is the first demonstration of a nucleotidylyltransferase discriminating between diastereomeric mixtures of sugar-1-phosphates to produce stereopure, biologically relevant furanosyl nucleotides. 相似文献
8.
GDP-2-, 3-, 4- or 6-azidomannoses can be successfully prepared from the corresponding azidomannose-1-phosphates and GTP using the enzyme GDP-Mannosepyrophosphorylase (GDP-ManPP) from Salmonella enterica and may serve as useful probes for mannosyltransferase activity. 相似文献
9.
Feng F Okuyama K Niikura K Ohta T Sadamoto R Monde K Noguchi T Nishimura S 《Organic & biomolecular chemistry》2004,2(11):1617-1623
Two non-natural fluorinated 2-N-acetamidosugar nucleotides, uridine 5'-diphosphate (UDP) 2-acetamido-2,4-dideoxy-4-fluoro-alpha-D-glucopyranose (UDP-4-FGlcNAc) 1 and its galacto isomer (UDP-4-FGalNAc) 2, were enzymatically constructed by treating chemically synthesized fluorinated 2-N-acetamidosugar 1-phosphates as the donor with UDP 2-acetamido-2-deoxy-alpha-D-glucopyranose pyrophosphorylase in the presence of uridine 5'-triphosphate (UTP). 相似文献
10.
The fungus Fusarium verticillioides is a pathogen of many plants and produces fumonisins. In addition to their well-studied animal toxicoses, these toxins contribute
to the development of maize seedling disease in susceptible maize varieties. Fumonisin disruption of sphingolipid biosynthesis
occurs during pathogenesis. An extraction method was developed for the simultaneous analysis of fumonisins B1 (FB1), B2 (FB2) and B3 (FB3), free sphingoid bases and sphingoid base 1-phosphates in maize tissues by liquid chromatography/linear ion trap tandem mass
spectrometry. The method involved a single extraction using 1:1 acetonitrile:water + 5% formic acid (1 ml per 10 mg tissue).
Mean recoveries ranged from approximately 50 to 99 percent, and limits of detection ranged from 10 fg μl−1 to 6900 fg μl−1. To test the efficacy of the method, seeds of a susceptible maize line were inoculated with a pathogenic, fumonisin-producing
strain of F. verticillioides. The seedlings were then harvested, and fumonisin content, as well as sphingoid bases and their 1-phosphates, were measured
in the leaf and root tissues. Fumonisin accumulation was significantly greater in leaf one compared to leaves two and three.
While FB1, FB2, and FB3 were detected in root tissues, FB1 was preferentially accumulated in leaf tissues. Accumulation of sphingoid bases and their 1-phosphates was evident in roots
and leaves of seedlings grown from inoculated seed, with the level of accumulation being similar in leaves 1, 2 and 3. The
method developed was effective, fast, and sensitive for use in simultaneously measuring fumonisin in tissues and their effects
on sphingolipid metabolite biomarkers of disease. The method should be useful for screening maize cultivars for susceptibility
to F. verticillioides-induced seedling diseases.
Figure Lesion with chromatography 相似文献
11.
Herein, we report an addition to the toolbox for the monitoring and quantification of the hydrolytic decay of pentose-1-phosphates, which are known to be elusive and difficult to quantify. This communication describes how apparent equilibrium shifts of a nucleoside phosphorolysis reaction can be employed to calculate hydrolytic loss of pentose-1-phosphates based on the measurement of post-hydrolysis equilibrium concentrations of a nucleoside and a nucleobase. To demonstrate this approach, we assessed the stability of the relatively stable ribose-1-phosphate at 98 °C and found half-lives of 1.8–11.7 h depending on the medium pH. This approach can be extended to other sugar phosphates and related reaction systems to quantify the stability of UV-inactive and hard-to-detect reaction products and intermediates. 相似文献
12.
The novel tetranuclear copper(II) complexes with alpha-d-glucose-1-phosphates, [Cu(4)(mu-OH)(alpha-d-Glc-1P)(2)(L)(4)(H(2)O)(2)](NO(3))(3) (L = bpy (1), phen (2)), were prepared and characterized by X-ray crystallography. Complex 1 was further transformed into the ATP stabilized tetracopper(II) complex of [Cu(4)(ATP)(2)(bpy)(4)] (4), where ATP is adenosine 5'-triphosphate. 相似文献
13.
A general one-step strategy is developed for the synthesis of hexofuranosyl 1-phosphates starting from new unprotected glycofuranosyl donors. It required first the preparation of new 1-thiohexofuranosides bearing a thioimidoyl heterocycle as a leaving group. The presence of sulfur and/or nitrogen atom(s) on the aglycon allowed remote activation of these thioglycofuranosides by anhydrous phosphoric acid and led to the target phosphates 9, 27, 29, and 30 in good to excellent selectivities and, more importantly, with very limited or no ring expansion. Moreover, this one-step phosphorylation reaction could be significantly improved by avoiding any tedious protecting group manipulations on negatively charged compounds and by focusing on a simple but general procedure of purification. This approach was applied to the diastereocontrolled synthesis of d-galacto- and d-glucofuranosyl 1-phosphates and also to the preparation of rare epimer and/or deoxy counterparts, that is, d-manno- and d-fucofuranosyl derivatives. 相似文献
14.
D. C. Dejongh S. C. Perricone M. L. Gay W. Korytnyk 《Journal of mass spectrometry : JMS》1968,1(1):151-166
The mass spectra of the different forms of vitamin B6, some metabolites and antimetabolites, and some analogs are reported. The free bases are suitable for study, but the 5-phosphates are not sufficiently volatile. The hydrochloride salts dissociate thermally in the inlet system into the free base and HCl and give the spectrum of the free base with the spectrum of HCL superimposed on it. The compounds studied are: pyridoxol, pyridoxamine and pyridoxal, which are different forms of vitamin B6; 4-pyridoxic acid and its lactone, 5-pyridoxic acid lactone, isopyridoxal, 5-formyl-3-hydroxy-2-methylpyridine-4-carboxylic acid, and 3-hydroxy-2-methylpyridine-4,5-dicarboxylic acid, which are vitamin B6 metabolites; α4-and α5-deoxypyridoxol, 3-deoxypyridoxol, and 4- and 5- norpyridoxol, which are antimetabolites and analogs of vitamin B6. 相似文献
15.
A synthesis of 1,2-cis-configurated, non-isosteric phosphonate analogues of aldose-1-phosphates is described. Treatment of 1-O-acyl-glycoses 1 , 7 , 13 , and 19 with trialkyl phosphite in the presence of trimethylsilyl trifluoromethanesulfonate gave the 1,2-cis-configurated glycosylphosphonates 2 , 4 , 8 , 10 , 14 , 16 , 20 , and 22 as the major anomers and the 1,2-trans-configurated glycosylphosphonates 3 , 5 , 9 , 11 , 15 , 17 , 21 , and 23 as the minor anomers. The 1,2-cis-configurated phosphonates 4 , 10 , 16 , and 22 were deprotected to give the (β-D -glucopyranosyl)phosphonate 6 , the (β-D -mannopyranosyl)phosphonate 12 , the (β-D -ribofuranosyl)phosphonate 18 , and the (β-D -arabinofuranosyl)phosphonate 24 , respectively, in high yields. The preferred formation of 1,2-cis-configurated phosphonates is explained by postulating an equilibrium between the anomeric phosphonium-salt intermediates (such as 25 and 26 ) and a stabilization of the cis-configurated salts through formation of a pentacoordinated species (such as 28 ). 相似文献
16.
Structure-based design of alkyl sugar-1-phosphates provides an efficient nucleotidylyltransferase-catalyzed synthesis of a series of new lipophilic sugar nucleotides possessing long or branched alkyl chains, thereby demonstrating the utility of nucleotidylyltransferases to catalyze the synthesis of sugar nucleotides with potential applications in lipopolysaccharide and lipoglycopeptide biosynthesis. 相似文献
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19.
Chiral 2′,3′,5′-trihydroxypentyl derivatives of adenine and cytosine in which configurations at C-2′ and C-3′ are opposite to those of the natural nucleosides have been synthesized. The nucleoside analogues were converted into 3′-phosphates and dinucleoside phosphate analogues with 3′–5′ phosphodiester linkages. PMR, UV and CD spectra of the compounds are presented. 相似文献
20.
The 1 : 1 intermediates generated by addition of isoquinoline to isocyanates were trapped by diphenyl phosphonate to yield diphenyl [2‐(aminocarbonyl)‐1,2‐dihydroisoquinolin‐1‐yl]phosphonates in good yields under solvent‐free conditions. 相似文献