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1.
The purple photosynthetic bacterium Rhodospirillum centenum has a putative type III polyketide synthase gene (rpsA). Although rpsA was known to be transcribed during the formation of dormant cells, the reaction catalyzed by RpsA was unknown. Thus we examined the RpsA reaction in vitro, using various fatty acyl‐CoAs with even numbers of carbons as starter substrates. RpsA produced tetraketide pyranones as major compounds from one C10–14 fatty acyl‐CoA unit, one malonyl‐CoA unit and two methylmalonyl‐CoA units. We identified these products as 4‐hydroxy‐3‐methyl‐6‐(1‐methyl‐2‐oxoalkyl)pyran‐2‐ones by NMR analysis. RpsA is the first bacterial type III PKS that prefers to incorporate two molecules of methylmalonyl‐CoA as the extender substrate. In addition, in vitro reactions with 13C‐labeled malonyl‐CoA revealed that RpsA produced tetraketide 6‐alkyl‐4‐hydroxy‐1,5‐dimethyl‐2‐oxocyclohexa‐3,5‐diene‐1‐carboxylic acids from C14–20 fatty acyl‐CoAs. This class of compounds is likely synthesized through aldol condensation induced by methine proton abstraction. No type III polyketide synthase that catalyzes this reaction has been reported so far. These two unusual features of RpsA extend the catalytic functions of the type III polyketide synthase family.  相似文献   

2.
A three-component reaction of benzaldehyde, 5,5-dimethyl-3-(arylamino)cyclohex-2-enone and 4-hydroxyquinolin-2(1H)-one gave a series of 3-((4,4-dimethyl-6-oxo-2-(arylamino) cyclohex-1-en-1-yl)(aryl)methyl)-4-hydroxyquinolin-2(1H)-one derivatives in ionic liquids at 80°C under catalyst-free conditions. In the presence of TsOH at 140°C, the same reaction provided an efficient method for the synthesis of 7-aryl-10,10-dimethyl-10,11-dihydro-5H-chromeno[3,2-c] quinoline-6,8(7H,9H)-dione derivatives in high yields while aromatic amine losing unexpectedly.  相似文献   

3.
The Liquid Phase Oxidation of Cyclohexene in Presence of Combinations of Compounds of Different Metals The oxidation of cyclohexene ( 1 ) with molecular oxygen in chlorobenzene solution at 80°C has been studied using cobalt, manganese and copper compounds, respectively in combination with molybdenum complexes. The selectivity has been determined of cyclohex-2-en-1-hydroperoxide ( 2 ), epoxycyclohexane ( 3 ), cyclohex-2-en-1-ol ( 4 ), cyclohex-2-en-1-one ( 5 ), 2,3-epoxy-cyclohexane-1-ol ( 6 ) and cyclohexane-1,2-diol ( 7 ), formed from reacted 1 . Investigation of the consecutive reactions showed that 3 and especially 4 can react in different ways and moreover 4 inhibits the oxidation of 1 . From these results conclusions were drawn on the mechanism of oxidation of 1 .  相似文献   

4.
The palladium-catalyzed reaction of iodobenzene, p-haloiodobenzenes (p-C6H4IX′; X′F, Cl, Br, I) and p-dibromobenzene with 4-vinylcyclohexene (Heck arylation reaction of olefins) was investigated with Pd(OAc)2/PR3/Et3N (R=phenyl, o-tolyl) as a classical catalyst system and with Pd(OAc)2/KOAc/[BzEt3N]Cl in DMF as a phase-transfer catalyst system, respectively. Iodobenzene reacts with 4-vinylcyclohexene to give (E)-2-(cyclohex-3-enyl) vinylbenzene ( 1 ) as main product. p-Haloiodobenzenes react with 4-vinylcyclohexene to give (E)-p-halo-2-(cyclohex-3-enyl) vinylbenzene ( 3 ), p-halo-1-(cyclohex-3-enyl) vinylbenzene ( 4 ) or (E,E)-p-bis[2-(cyclohex-3-enyl)vinyl]benzene ( 5 ) depending on the reaction conditions and the catalyst system used. The phase-transfer catalyst system is less reactive but more selective. A reaction temperature of 80°C is necessary for reaction with p-dibromobenzene. The investigations demonstrate the much higher reactivity of the exocyclic double bond of 4-vincylcyclohexene in comparison with the endocyclic one.  相似文献   

5.
唐建生  莫敏  郑敏 《化学世界》2013,54(3):169-171,192
以N,N-二甲基甲酰胺作溶剂,2-对甲苯乙炔基苯酚和α-环己烯酮在氯化钯和四丁基碘化铵的作用下,可以顺利发生分子内环化反应一步合成3-(2-对甲苯基苯并呋喃-3-基)环己-2-烯酮。反应最佳条件为:n(2-对甲苯乙炔基苯酚)∶n(α-环己烯酮)∶n(氯化钯)∶n(四丁基碘化铵)=1∶5∶0.05∶1,反应温度为100℃,反应时间为24h,反应最佳产率82.0%。产物经1 H NMR、13 CNMR和GC-MS确征。  相似文献   

6.
Transformation of (20S)-20-(Hydroxymethyl)pregna-1,4-dien-3-one into (20S)-20-(p-Toluene-sulfonyloxymethyl)pregna-1,5-dien-3β-ol and -3α-ol: Intermediates of Vitamin D Derivatives Efficient three-step approaches to the two 3-epimeric 22-tosylated 1,5-diene-3,22-diols 6 and 7 starting with (20S)-20-(hydroxymethyl)pregna-1,4-dien-3-one ( 1 ) were developed and optimized. Isomerization of 1 to the 1,5-dien-3-one 3 and subsequent tosylation furnished the deconjugated 3-ketone 4 . The 3β-alcohol 6 was available from 4 by means of in situ generated calcium borohydride. Treatment of 4 with lithium trisiamylborohydride (LS-Selectride) afforded the highest yield of the hitherto unknown 3α-epimer 7 . Following the optimized synthesis, 6 and 7 were obtained from 1 in 60 % and 50 % overall yield, respectively.  相似文献   

7.
The enzymatic transglycosylation of 2,6‐dichloropurine (26DCP) and 6‐chloro‐2‐fluoropurine (6C2FP) with uridine, thymidine and 1‐(β‐D ‐arabinofuranosyl)‐uracil as the pentofuranose donors and recombinant thermostable nucleoside phosphorylases from G. thermoglucosidasius or T. thermophilus as biocatalysts was studied. Selection of 26DCP and 6C2FP as substrates is determined by their higher solubility in aqueous buffer solutions compared to most natural and modified purines and, furthermore, synthesized nucleosides are valuable precursors for the preparation of a large number of biologically important nucleosides. The substrate activity of 26DCP and 6C2FP in the synthesis of their ribo‐ and 2′‐deoxyribo‐nucleosides was closely similar to that of related 2‐amino‐ (DAP), 2‐chloro‐ and 2‐fluoroadenines; the efficiency of the synthesis of β‐D ‐arabinofuranosides of 26DCP and 6C2FP was lower vs. that of DAP under similar reaction conditions. For a convenient and easier recovery of the biocatalysts, the thermostable enzymes were immobilized on MagReSyn® epoxide beads and the biocatalyst showed high catalytic efficiency in a number of reactions. As an example, 6‐chloro‐2‐fluoro‐(β‐D ‐ribofuranosyl)‐purine ( 9 ), a precursor of various antiviral and antitumour drugs, was synthesized by the immobilized enzymes at 60 °C under high substrate concentrations (uridine:purine ratio of 2:1, mol). The synthesis was successfully scaled‐up [uridine (2.5 mmol), base (1.25 mmol); reaction mixture 50 mL] to afford 9 in 60% yield. The reaction reveals the great practical potential of this enzymatic method for the efficient production of modified purine nucleosides of pharmaceutical interest.

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8.
The triacylglycerol of Crambe abyssinica seeds consist of 95 % very long chain (>18 carbon) fatty acids (86 % erucic acid; 22:1?13) in the sn‐1 and sn‐3 positions. This would suggest that C. abyssinica triacylglycerols are not formed by the action of the phospholipid:diacylglycerol acyltransferase (PDAT), but are rather the results of acyl‐CoA:diacylglycerol acyltransferase (DGAT) activity. However, measurements of PDAT and DGAT activities in microsomal membranes showed that C. abyssinica has significant PDAT activity, corresponding to about 10 % of the DGAT activity during periods of rapid seed oil accumulation. The specific activity of DGAT for erucoyl‐CoA had doubled at 19 days after flowering compared to earlier developmental stages, and was, at that stage, the preferred acyl donor, whereas the activities for 16:0‐CoA and 18:1‐CoA remained constant. This indicates that an expression of an isoform of DGAT with high specificity for erucoyl‐CoA is induced at the onset of rapid erucic acid and oil accumulation in the C. abyssinica seeds. Analysis of the composition of the acyl‐CoA pool during different stages of seed development showed that the percentage of erucoyl groups in acyl‐CoA was much higher than in complex lipids at all stages of seed development except in the desiccation phase. These results are in accordance with published results showing that the rate limiting step in erucic acid accumulation in C. abyssinica oil is the utilization of erucoyl‐CoA by the acyltransferases in the glycerol‐3‐phosphate pathway.  相似文献   

9.
4-Phenyl-5-aminopyrazole 2 obtained from phenylcyanoacetaldehyde 1 and hydrazine hydrate reacted with diethyl malonate to give 3-phenyl-5,7-dioxopyrazolo[1,5-a]pyrimidine 3 , used as the key compound in the synthesis of arylazo dyes. The key compound 3 was coupled with various aryldiazonium salts 4 to yield 3-phenyl-7-hydroxy-6-arylazopyrazolo[1,5-a]pyrimid-5-ones 5. The resulting arylazo dyes (5) were refluxed in phosphorus oxychloride to give 3-phenyl-5,7-dichloro-6-arylazo-pyrazolo[1,5-a]pyrimidines 6 , which subsequently reacted with refluxing morpholine and piperidine to yield 3-phenyl-5,7-bis(morpholino and piperidino)-6-aryiazopyrazolo[1,5-a]pyrimidines 7. The arylazo dyes 5 and 7 were applied to polyester fibres as disperse dyes and the arylazo dyes 6 were applied to polyamide fibres as disperse reactive dyes. The spectral and dyeing properties of the dyes were studied.  相似文献   

10.
The metabolism of benzo[c]chrysene (B[c]Ch) with various cytochrome P450 (CYP) enzymes including rat 1A1, 1A2, 2B1 and 2E1, human 1A1, 1A2, 2A6, 1B1, 3A4 and 2E1, mouse 1B1, and scup fish 1A1 expressed in Chinese hamster V79 cells has been investigated to clarify the role of individual enzymes in the regioselective oxidation of B[c]Ch and the species dependency. In six cell lines expressing individual CYP enzymes from four different species B[c]Ch was metabolized to several isomeric phenols and trans?dihydrodiols. However, cell lines expressing human 3A4, 2A6 and 2E1 or rat 1A2, 2B1 and 2E1 were metabolically in-competent towards B[c]Ch. Among the trans?dihydrodiols the 9,10-isomer could be detected in cells expressing human, rat and fish CYP 1A1 and to a minor extent in cells with human 1A2, but not in cells expressing human and mouse CYP 1B1. The latter two cell lines produced high amounts of the bay region 3,4-dihydrodiol, whereas the K-region 7,8-dihydrodiol was a minor metabolite. Oxidation of B[c]Ch to the 1,2-dihydrodiol could not be catalyzed by any of the CYP enzymes investigated except fish 1A1. Our results suggest that metabolic activation of B[c]Ch is initiated predominantly by CYP 1A1 to result selectively in the formation of fjord region 9,10-dihydrodiol 11,12-epoxides regardless of the species involved. The activation of B[c]Ch appears to be limited by a low regioselectivity for the 9,10-oxidation.  相似文献   

11.
Upon treatment with KF in acetonitrile the zwitterionic Meisenheimer complexes 3 undergo β-elimination leading to potassium 7-(2-aryl-2-oxo-ethylidene)-4,6-dinitro-7,x-dihydrobenzofurazanide 1-oxides 4 in 72–87% yield. Compounds 4 give 7-(2-aryl-2-oxo-ethyl)-4,6-dinitrobenzofuroxans 6 when treated with hydrochloric acid. 4-(2-Aryl-1-dimethylsulfonio-2-oxo-ethylidene)-5,7-dinitro-4,x-dihydrobenzofurazanides 5 are obtained by reaction of 3 with sodium methoxide. The structure of 5e is confirmed by X-ray structure analysis. The reaction of complexes 8 with acetic acid/potassium acetate at 80°C affords 4-(2-aryl-2-oxo-1-pyridinio-ethylidene)-5,7-dinitro-4,x-dihydrobenzofurazanides 9 in moderate yields.  相似文献   

12.
Bis-(1-chloro-3-phenoxy-prop-2-yl)-sulfanes – Nucleophilic Displacement and Regiochemistry. Separation and Assignment of Diastereomers. Synthesis of Diastereomerically Pure Trithiacycles The title compounds 1 were substituted by a series of O-, N- and S-nucleophiles (H2O solvolysis, AgOAc, NaN3, KSCN, NaSPh, thiourea). A strong tendency to β-elimination of HCl depending on the kind of the attacking nucleophile was found. In most cases no regioisomerization could be detected in the isolated products of the nucleophilic displacement. Best results were obtained with sulfur nucleophiles. The separation of the diastereomeric mixture of the p-kresyl derivative 1b into the individual diastereomers 1bA and 1bB in a preparative scale was achieved. These 3-thia-1,5-dichlorides and several products of substitution could be assigned to the meso- or (±)-form by examination of the stereochemistry and symmetry of the corresponding sulfoxides. The 1,5-dimercapto derivatives 8 are convenient as structural units for the synthesis of diastereomerically pure cis- or trans-disubstituted trithiacycles e.g. 15bA , 15bB . The (±)-form of the 4,6-disubstituted 2,5,8-trithia[9]-(2,6)-pyridinophane 16bA was characterized by X-ray crystal structure determination.  相似文献   

13.
A straightforward assisted tandem palladium(II)‐ and palladium(0)‐catalyzed direct C‐3 and N‐4 arylation of quinoxalin‐2(1 H)‐ones with boronic acids and aryl halides in water as safe and cheap solvent is reported. This environmentally friendly catalytic protocol is compatible with a wide range of functional groups and allows construction of various biologically important quinoxalin‐2(1 H)‐one backbones.

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14.
The three major components of setal exudate from nymphs of the Hawthorn lace bug,Corythucha cydoniae, were identified as 3,6-dihydroxy-2-[1-oxo-6(E),8(E)-tetradecadienyl]cyclohex-2-en-1-one; 3,6-dihydroxy-2-[1-oxo-dodecanyl]-cyclohex-2-en-1-one; 3,6-dihydroxy-2-[1-oxo-8-dodecenyl] cyclohex-2-en-1-one. An additional 10 minor components were partially characterized.  相似文献   

15.
Zi-Wei Ye  Mee-Len Chye 《Lipids》2016,51(1):1-13
A gene family encoding six members of acyl‐CoA‐binding proteins (ACBP) exists in Arabidopsis and they are designated as AtACBP1–AtACBP6. They have been observed to play pivotal roles in plant lipid metabolism, consistent to the abilities of recombinant AtACBP in binding different medium‐ and long‐chain acyl‐CoA esters in vitro. While AtACBP1 and AtACBP2 are membrane‐associated proteins with ankyrin repeats and AtACBP3 contains a signaling peptide for targeting to the apoplast, AtACBP4, AtACBP5 and AtACBP6 represent the cytosolic forms in the AtACBP family. They were verified to be subcellularly localized in the cytosol using diverse experimental methods, including cell fractionation followed by western blot analysis, immunoelectron microscopy and confocal laser‐scanning microscopy using autofluorescence‐tagged fusions. AtACBP4 (73.2 kDa) and AtACBP5 (70.1 kDa) are the largest, while AtACBP6 (10.4 kDa) is the smallest. Their binding affinities to oleoyl‐CoA esters suggested that they can potentially transfer oleoyl‐CoA esters from the plastids to the endoplasmic reticulum, facilitating the subsequent biosynthesis of non‐plastidial membrane lipids in Arabidopsis. Recent studies on ACBP, extended from a dicot (Arabidopsis) to a monocot, revealed that six ACBP are also encoded in rice (Oryza sativa). Interestingly, three small rice ACBP (OsACBP1, OsACBP2 and OsACBP3) are present in the cytosol in comparison to one (AtACBP6) in Arabidopsis. In this review, the combinatory and distinct roles of the cytosolic AtACBP are discussed, including their functions in pollen and seed development, light‐dependent regulation and substrate affinities to acyl‐CoA esters.  相似文献   

16.
Epoxyketone proteasome inhibitors have attracted much interest due to their potential as anticancer drugs. Although the biosynthetic gene clusters for several peptidyl epoxyketone natural products have recently been identified, the enzymatic logic involved in the formation of the terminal epoxyketone pharmacophore has been relatively unexplored. Here, we report the identification of the minimal set of enzymes from the eponemycin gene cluster necessary for the biosynthesis of novel metabolites containing a terminal epoxyketone pharmacophore in Escherichia coli, a versatile and fast‐growing heterologous host. This set of enzymes includes a non‐ribosomal peptide synthetase (NRPS), a polyketide synthase (PKS), and an acyl‐CoA dehydrogenase (ACAD) homologue. In addition to the in vivo functional reconstitution of these enzymes in E. coli, in vitro studies of the eponemycin NRPS and 13C‐labeled precursor feeding experiments were performed to advance the mechanistic understanding of terminal epoxyketone formation.  相似文献   

17.
以1,5-二氯-2,4-二硝基苯(DCDNB)为原料,经烷氧基化和催化加氢还原反应合成4,6-二乙氧基间苯二胺(DEDAB),并探索了其影响因素。结果表明合成中间体1,5-二乙氧基-2,4-二硝基苯(DEDNB)的较佳条件为:n(DCDNB)∶n(NaOH)∶n(无水C2H5OH)=1∶4∶30,室温下反应7 h,收率96.43%,HPLC纯度99.74%;产品DEDAB的较优合成工艺条件为:n(DEDNB)∶n(无水C2H5OH)= 1∶44,w(10%Pd/C)/w(DEDNB)= 10%,反应时间7 h,反应温度110 ℃,氢气压力1.5 MPa,收率95.42%,HPLC纯度98.87%。产品及中间体结构经1H NMR、MS 和FTIR分析表征确认。  相似文献   

18.
Glycidol was biologically derivatized by the unspecific wax ester synthase/acyl coenzyme A (acyl‐CoA): diacylglycerol acyltransferase (WS/DGAT) from Acinetobacter baylyi ADP1 into glycidyl acyl ester. Catalysis of in vitro conversion of glycidol to glycidyl acyl ester by the WS/DGAT from A. baylyi was verified by (i) a radiometric assay, (ii) thin‐layer chromatography and (iii) also by ESI‐MS. A specific activity of 50 nmol·mg–1·min–1 was obtained when 10 mM glycidol and 5 µM palmitoyl‐CoA were used. In vivo synthesized glycidyl acyl esters in recombinant E. coli were detected and quantified by staining with the epoxide‐specific reagent 4‐(4‐nitrobenzyl)‐pyridine. Of glycidyl acyl esters, 1.5 mg/L was obtained from the culture in the presence of 10 mM glycidol and 10 mM oleate.  相似文献   

19.
4-Aminoantipyrine was utilized as key intermediate for the synthesis of pyrazolone derivatives bearing biologically active moieties. The newly synthesized compounds were characterized by IR, 1H- and 13C-NMR spectral and microanalytical studies. The compounds were screened as anticancer agents against a human tumor breast cancer cell line MCF7, and the results showed that (Z)-4-((3-amino-5-imino-1-phenyl-1H-pyrazol-4(5H)-ylidene)methylamino)-1,5-dimethyl-2-phenyl-1,2-dihydropyrazol-3-one 5, 3-(4-bromophenyl) -1-(1,5-dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-yl)-4-oxo-2-thioxo-1,2,3,4-tetrahydropyrimidine-5-carbonitrile 13, 1-(1,5-dimethyl-3-oxo-2-phenyl-2,3-dihydro-1-Hpyrazol- 4-yl)-3-(4-iodophenyl)-4-oxo-2-thioxo-1,2,3,4-tetrahydropyrimidine-5-carbonitrile 14, 3,3′-(4,4′-sulfonylbis(4,1-phenylene))bis(1-(1,5-dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol- 4-yl)-4-oxo-2-thioxo-1,2,3,4-tetrahydropyrimidine-5-carbonitrile) 16, (Z)-1-(1,5-dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-yl)-2-hydrazono-4-oxo-3-phenyl-1,2,3,4-tetrahydropyrimidine-5-carbonitrile 17, (Z)-1-(1,5-dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-yl)-4-oxo-3-phenyl-2-(2-phenylhydrazono)-1,2,3,4-tetrahydro pyrimidine-5-carbonitrile 18, and (Z)-4-(3-amino-6-hydrazono-7-phenyl-6,7-dihydro pyrazolo[3,4-d]pyrimidin-5-yl)-1,5-dimethyl-2-phenyl-1,2-dihydropyrazol-3-one 19 were the most active compounds with IC50 values ranging from 30.68 to 60.72 μM compared with Doxorubicin as positive control with the IC50 value 71.8 μM.  相似文献   

20.
The nitrile reductase QueF catalyzes NADPH-dependent reduction of the nitrile group of preQ0 (7-cyano-7-deazaguanine) into the primary amine of preQ1 (7-aminomethyl-7-deazaguanine), a biologically unique reaction important in bacterial nucleoside biosynthesis. Here we have discovered that the QueF from Escherichia coli—its D197A and E89L variants in particular (apparent kcat≈10−2 min−1)—also catalyze the slow hydration of the C5=C6 double bond of the dihydronicotinamide moiety of NADPH. The enzymatically C6-hydrated NADPH is a 3.5:1 mixture of R and S forms and rearranges spontaneously through anomeric epimerization (β→α) and cyclization at the tetrahydronicotinamide C6 and the ribosyl O2. NADH and 1-methyl- or 1-benzyl-1,4-dihydronicotinamide are not substrates of the enzymatic hydration. Mutagenesis results support a QueF hydratase mechanism, in which Cys190—the essential catalytic nucleophile for nitrile reduction—acts as the general acid for protonation at the dihydronicotinamide C5 of NADPH. Thus, the NADPH hydration in the presence of QueF bears mechanistic resemblance to the C=C double bond hydration in natural hydratases.  相似文献   

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