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991.
Joncour A Décor A Liu JM Dau ME Baudoin O 《Chemistry (Weinheim an der Bergstrasse, Germany)》2007,13(19):5450-5465
The asymmetric synthesis of novel axially chiral biaryl compounds 5 a-f containing a seven- or eight-membered heterocyclic medium ring is described. These molecules can be considered to be structural hybrids of allocolchicine- and steganacin-type natural products. The synthesis featured an atropo-diastereoselective biaryl Suzuki coupling in which a benzylic stereocenter efficiently transferred its stereochemical information to the biaryl axis. The coupling conditions were optimized, and two biphenylphosphane ligands (DavePhos and S-Phos) were found to give the highest yields and diastereoselectivities. A three-element stereochemical model was proposed to explain the observed diastereoselectivities. In a second key step, the medium ring of the target molecules was formed by a stereoselective S(N)1-type cyclodehydration that probably involved a configurationally stable carbocationic intermediate, as supported by calculations. Alternatively, S(N)2-type cyclizations were employed on the same Suzuki coupling products to give the target molecules in a stereodivergent or stereoconvergent manner. These cyclization methods furnished the target hybrid analogues 5 a-f with ee values above 94 %. All analogues were evaluated as antimicrotubule agents and against a panel of cancer-cell lines using colchicine (1) and N-acetylcolchinol (3) as references. Promising activities were found for R,aR-configured compounds 5 a, b and 5 f; in particular, ethyl analogue 5 b showed a twofold antimicrotubule activity relative to colchicine. 相似文献
992.
Seggio A Lannou MI Chevallier F Nobuto D Uchiyama M Golhen S Roisnel T Mongin F 《Chemistry (Weinheim an der Bergstrasse, Germany)》2007,13(35):9982-9989
Metalation of N-phenylpyrrole by using an in situ mixture of ZnCl(2)TMEDA (0.5 equiv; TMEDA=N,N,N',N'-tetramethylethylenediamine) and LiTMP (1.5 equiv; TMP=2,2,6,6-tetramethylpiperidino) was optimized. The reaction carried out at room temperature in THF resulted in incomplete metalation (56 % conversion) and selectivity (mixture of 2-iodo and 2,2'-diiodo derivatives in an 86:14 ratio after trapping with iodine). By using diethyl ether (DEE), toluene, or hexane instead of THF, low conversions of 17, 38, or 23 % were observed, respectively, but the formation of the diiodide was avoided. When hexane was used as solvent, strong lithium-complexing ligands such as [12]crown-4 and N,N'-dimethylpropylideneurea (DMPU) inhibited the reaction whereas more (hemi)labile ligands (TMEDA>THF approximately DME) favored it. This result shows that a temporary accessibility of lithium to interact with the rest of the base and/or the substrate is a prerequisite for an efficient metalation. A 75 % yield of 2-iodo-N-phenylpyrrole was obtained after reaction with the base in the presence of five equivalents of TMEDA for two hours at room temperature, and subsequent trapping with iodine. We were able to successfully replace the spare TMP with a less expensive butyl group. 相似文献
993.
Deveson A 《Chemistry (Weinheim an der Bergstrasse, Germany)》2007,13(19):5318-5321
994.
Wind M Gebhardt K Grunwald H Spickermann J Donzelli M Kellenberger L Muller M Fullhardt P Schmitt-Hoffmann A Schleimer M 《Rapid communications in mass spectrometry : RCM》2007,21(7):1093-1099
The in vitro metabolic pattern of BAL19403, a novel macrolide antibiotic, was investigated by capillary liquid chromatography/quadrupole time-of-flight mass spectrometry (LC/QTOF-MS) in incubations with human microsomes. For the elucidation of the metabolic pathway, BAL19403 labeled with four deuterium atoms (D4) was used, and detection of metabolites performed using mixtures of the unlabeled (H4) BAL19403 and its D4 analogue (1:1) as substrate. All metabolites appeared with similar chromatographic behavior. MS/MS spectra of BAL19403 and its metabolites are dominated by non-informative fragment ions. Therefore, the structure of the metabolites was elucidated mainly by accurate mass measurements with subsequent proposals of elemental compositions. Main biotransformations were N-demethylation, lactone ring hydrolysis, and oxidation. Additionally, N-dealkylation of the aromatic moiety was identified. This dealkylation results not only in formation of an aldehyde, according to the classical pathway, but also in formation of the corresponding alcohol and carboxylic acid. Final elucidation of their structures was possible, since this dealkylation takes place vicinal to the deuterium-labeled part of BAL19403 and interferes with D/H exchange. The degree of D/H exchange, determined by analysis of the metabolite isotopic pattern, was used to elucidate the adjacent functional group. 相似文献
995.
Le Nestour A Gaudon M Villeneuve G Daturi M Andriessen R Demourgues A 《Inorganic chemistry》2007,46(10):4067-4078
Zn1-xCuxAl2O4 (0 < or = x < 0.30) compounds have been synthesized by polyesterification using metallic salts and annealing at low temperatures as well as by conventional solid state. XRD-powder data refinements (Rietveld method) have demonstrated that both compound series crystallize in the spinel structure (Fd3m) and exhibit similar inversion rates. This low-temperature route lead to metastable phases with crystallite sizes around 40 nm whereas particle sizes are larger than 1 moicrom in the case of solid-state route. This preparative method largely described in the literature allows stabilizing reduced copper states thanks to the presence of reductive organic species, which are decomposed below T = 700 degrees C. The absorption spectra of the x = 0.15 composition exhibit strong differences depending on the synthesis route. These differences can be explained by the occurrence of Cu2+/Cu+ mixed valencies in compounds prepared by the low-temperature route; 33% of monovalent copper has been identified in the x = 0.15 composition prepared by low-temperature process, whereas the solid-state compound contains only divalent copper. Reductive properties of polyesterification reaction implying citric acid and low annealing temperature (T = 700 degrees C) are mainly responsible of the occurrence of the Cu2+/Cu+ mixed valencies. Actually, the annealing under air at T = 1000 degrees C of divided zinc-copper aluminates prepared at low temperatures (T = 700 degrees C) leads to the oxidation reaction Cu+ --> Cu2+ + e- confirmed by the evolution of magnetic measurements, ESR spectra, and optical absorption properties. Defects such as oxygen vacancies in the anionic network leading to reduction in the cations coordination number could also explain the strong evolution of optical absorption spectra especially around lambda = 700 nm where intervalencies transfer (Cu+/Cu2+) as well as intra-atomic d-d transitions (Cu2+ in a 5-fold coordination) can occur. Finally the occurrence of monovalent and divalent copper at the surface of such divided oxides, probably in tetrahedral sites, has been demonstrated by FTIR spectroscopy using the co-adsorption of CO and NO as probe molecules. 相似文献
996.
The normally weak process of hyper-Raman scattering can be greatly enhanced when the excitation is two photon resonant with an electronic transition that is both one and two photon allowed. It might be expected to be further enhanced when a one-photon allowed transition provides an intermediate state resonance in the two-photon excitation step. The theory of this triply resonant process is developed for organic nonlinear chromophores. Experimental results are obtained for one donor-acceptor substituted push-pull chromophore in which the energy of the strongly allowed lowest-lying one-photon state may be tuned by varying the solvent without substantially affecting the two-photon resonant transition. Surprisingly, bringing the one-photon allowed state into resonance does not significantly increase the hyper-Rayleigh or hyper-Raman hyperpolarizabilities. Analysis of the resonance Raman, hyper-Rayleigh, and hyper-Raman profiles suggests that the triply resonant path does not make the dominant contribution to the hyperpolarizability in this system. 相似文献
997.
Kranz B Bürck J Franzreb M Köster R Ulrich AS 《Journal of colloid and interface science》2007,316(2):413-419
Circular dichroism (CD) was used to characterize the secondary structure of penicillin G acylase upon covalent immobilization on silica nanoparticles. Covalent immobilization was achieved by functionalizing the silica nanoparticles with glutardialdehyde and coupling to the free NH(2) groups of the enzyme (lysine and arginine side chains). The loading of the covalently bound enzyme was increased up to saturation, which was reached at 54.6 mg immobilized enzyme per g silica nanobeads. For structural characterization of the commercially available enzyme its exact molecular mass was determined by mass spectrometry in order to enable precise evaluation of the CD data. The fraction of secondary structure elements of the free and immobilized enzyme were estimated from the respective CD spectra using standard algorithms (CONTINLL, CDSSTR, SELCON3). The fractions obtained by the different algorithms for the free enzyme agreed well with one another and also with data from X-ray diffraction described in the literature. Interestingly, the secondary structure fractions found for the immobilized enzyme were very similar to the free enzyme and nearly constant over all experiments. These results indicate that even a loading of up to 55.8 mg/g (enzyme per silica nanoparticles) causes only slight structural changes. However, the specific activity determined by a kinetic assay decreased by around 60%, when increasing the loading from 14.9 to 55.8 mg/g. Because of the fact that we found no major changes in the secondary structure, diffusion limitation seems to be the main reason for the decline of the specific activity. 相似文献
998.
Adsorption of proteins on surfaces of hydrophobic interaction chromatography media is at least a two-stage process. Application of pure protein pulses (bovine serum albumin and beta-lactoglobulin) to hydrophobic interaction chromatography media yielded two chromatographic peaks at low salt concentrations. At these salt concentrations, the adsorption process is affected by a second reaction, which can be interpreted as protein spreading or partial unfolding of the protein. The kinetic constants of the spreading reaction were derived from pulse response experiments at different residence times and varying concentrations by applying a modified adsorption model considering conformational changes. The obtained parameters were used to calculate uptake and breakthrough curves for spreading proteins. Although these parameters were determined at low saturation of the column, predictions of overloaded situations could match the experimental runs satisfactorily. Our findings suggest that proteins which are sensitive to conformational changes should be loaded at high salt concentrations in order to accelerate the adsorption reaction and to obtain steeper breakthrough curves. 相似文献
999.
A convenient and selective TLC of 4-R-1,2,4-triazoles (Rtrz) and nitrogen containing aromatic rings is presented (molecules 1-11). This simple revelation method implies a complexation of heterocycles to Co(II) ions on a TLC plate, followed by a subsequent modification of the reduction potential which enables oxidation of Co(II) by permanganate. 相似文献
1000.
The reactivity of 3‐nitro‐4‐pyridyl isocyanate ( 7 ) and 5‐nitropyridin‐2‐yl isocyanate ( 9 ) in 1,3‐dipolar cycloaddition reactions with azides and pyridine N‐oxides has been investigated. 1,3‐Dipolar cycloaddition to trimethylsilylazide (TMSA) afforded the respective tetrazolinones, 1‐(3‐nitropyridin‐4‐yl)‐1H‐tetrazol‐5(4H)one ( 8 , 50 %) and 1‐(5‐nitropyridin‐2‐yl)‐1H‐tetrazol‐5(4H)one ( 11 , 64 %). Respectively, 1,3‐dipolar cycloaddition of nitropyridyl isocyanates 7 and 9 to 3,5‐dimethylpyridine N‐oxide ( 14 ), 3‐methylpyridine N‐oxide ( 21 ) and pyridine N‐oxide ( 22 ) gave the substituted amines, 3,5‐dimethyl‐N‐(3‐nitropyridin‐4‐yl)pyridin‐2‐amine ( 17 ), 3,5‐dimethyl‐N‐(5‐nitropyridin‐2‐yl)pyridin‐2‐amine ( 20 ), N‐(5‐nitropyridin‐2‐yl)pyridin‐2‐amine ( 24 ), 5‐methyl‐N‐(5‐nitropyridin‐2‐yl)pyridin‐2‐amine ( 23 ) and 3‐methyl‐N‐(5‐nitropyridin‐2‐yl)pyridin‐2‐amine ( 25 ) in 65 ‐ 80 % yield, obtained by cycloaddition, rearrangement and decarboxylation. The results demonstrate that the nitropyridyl isocyanates ( 7,9 ) readily undergo 1,3‐dipolar cyloaddition reactions similar to phenyl isocyanates. 相似文献