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In this paper we describe enantioselective syntheses of (+)-carbapentostatin (8) and its cyclopentyl analogue 12b. A new and efficient one-pot, two-step preparation of aldehyde 15 has been developed, based on the borane reduction of N-Pf-protected L-aspartic acid gamma-methyl ester (13) and Swern oxidation of the resulting alcohol. Homologation to diester 18 and ring formation by Dieckman cyclization, followed by reduction and dehydration steps, afford the 4-amino-1-cyclopentenemethanol derivative 22. Hydroboration and oxidation transform this compound stereospecifically into aminocyclopentanol 26, the key aminocyclitol component for an asymmetric synthesis of (+)-carbapentostatin. 相似文献
3.
Subbiah Meenakshisundaram RM. Sockalingam 《Journal of molecular catalysis. A, Chemical》2000,160(2):269-275
Catalytic activity of Os(VIII) in the oxidation of some twenty organic sulfides with sodium salt of N-chlorobenzenesulfonamide (CAB) has been investigated in alkaline (pH8.7) t-butanol–water (1:1 v/v) medium. Significant retarding influence of [OH−] on the reactivity is exhibited. The catalysed reaction is strongly accelerated in the presence of Hg(II). Imperfections are observed in the linear Hammett relationship in the case of –NO2 substituents. 相似文献
4.
This research work is concerned with the use of N‐benzoyl cyanoacetylhydrazine ( 3 ) in synthesizing several new heterocyclic compounds with potential biological activity, via its reaction with various chemical reagents. The synthesized derivatives have actually exhibited, upon screening, antibacterial and antifungal activities. 相似文献
5.
Kinetics of the reaction of methyl 4‐nitrobenzenesul‐fonate + Br− in ethanol amine based surfactants
The kinetics of the reaction of methyl 4‐nitrobenzenesulfonate + Br? ions has been studied in ethanol amine based (alkyldimethylethanolammonium bromide and alkyldiethylethanolammonium bromide) surfactant solutions. The observed first‐order rate constants increase monotonically with surfactant concentration, with hydrophobic chain length and with head group bulk in a manner similar to other quaternary ammonium surfactants. The results were analyzed using the pseudophase model of micellar rate effects in conjunction with a Langmuir form to describe micellar binding of bromide ion. An attempt to estimate activation parameters of the reaction from temperature variance of micellar pseudophase rate constants has also been made. © 2006 Wiley Periodicals, Inc. Int J Chem Kinet 38: 303–308, 2006 相似文献
6.
Nano titanium dioxide (nTiO2), generally considered to be toxicologically inert, is manufactured in large quantities and extensively applied in consumer products. The small size and large surface area endow them with an active group or intrinsic toxicity. Advances in instrumentation are making Raman spectroscopy the tool of choice for an increasing number of (bio) chemical applications. One of the great advantages of this technique is its ability to provide information on the concentration, structure and interaction of biochemical molecules in their microenvironments within intact cells and tissues, non-destructively. Zebrafish (Danio rerio), one of the most important vertebrate model organisms used in developmental biology, are increasingly used in biomedical research, particularly as a model of human disease. In the present work, an attempt is made to study the effect of titanium dioxide, both nano and bulk, on the microenvironment of the liver tissues of Zebrafish using FT-Raman spectroscopy. The results of the present study suggest that TiO2 exposure demonstrate a marked influence on the microenvironments of the liver tissues of Zebrafish. A shift to a higher wavenumber and an increase in the intensity of the band at ∼1087 cm−1 in the TiO2 exposed tissues suggest that some of the conformational changes resulting from the alkali recovery process takes place due to TiO2 exposure. The decreased intensity ratio (I3220/I3400) observed in the titanium-exposed tissues suggests a decreased water domain size, which could be interpreted in terms of weaker hydrogen-bonded molecular species of water in the TiO2 exposed tissues. The observed shift of COO− bands to higher frequencies shows the disruption of salt bridges as a result of a change in the oppositely charged partners and due to the enhanced random coil conformation. The variation in the intensity ratio of the tyrosyl doublet (I858/I825) indicates variation in the hydrogen bonding of the phenolic hydroxyl group due to TiO2 exposure. The results further suggest that the microenvironments are greatly altered due to titanium nano exposure when compared to titanium bulk. In conclusion, the results indicate that FT-Raman spectroscopy might be a useful tool for rapid assessment of nano particle biological interactions. 相似文献
7.
Jackson DR Mohareb A MacNeil J Razul MS Marangoni DG Poole PH 《The Journal of chemical physics》2011,134(20):204503
Using a 2D lattice model, we conduct Monte Carlo simulations of micellar aggregation of linear-chain amphiphiles having two solvophilic head groups. In the context of this simple model, we quantify how the amphiphile architecture influences the critical micelle concentration (CMC), with a particular focus on the role of the asymmetry of the amphiphile structure. Accordingly, we study all possible arrangements of the head groups along amphiphile chains of fixed length N = 12 and 16 molecular units. This set of idealized amphiphile architectures approximates many cases of symmetric and asymmetric gemini surfactants, double-headed surfactants, and boloform surfactants. Consistent with earlier results, we find that the number of spacer units s separating the heads has a significant influence on the CMC, with the CMC increasing with s for s < N/2. In comparison, the influence of the asymmetry of the chain architecture on the CMC is much weaker, as is also found experimentally. 相似文献
8.
Facile syntheses of pyrazole, pyridine, pyrimidine and pyrazolo[3,4-d]pyrimidine derivatives have been achieved by the reaction of β-enamino nitrile 2a with hydrazines, phenyl isothiocyanate, thiourea and active methylene reagents. The β-enamino ketone 2e with the same reagents affords 3,5-dimethyl heterocyclic ring systems. 相似文献
9.
Amira E.M. Abdallah Rafat M. Mohareb Ebtsam A. Ahmed 《Journal of heterocyclic chemistry》2019,56(11):3017-3029
Preparation of pyrano[2,3‐d]thiazole and thiazolo[4,5‐b]pyridine derivatives through multicomponent reactions (MCRs) was achieved by the reaction of 2‐(2‐amino‐4,5,6,7‐tetrahydrobenzo[b]thiophen‐3‐yl)thiazol‐4(5H)‐one with various active methylene reagents such as ethyl cyanoacetate or malononitrile in basic conditions containing diverse aromatic aldehyde. Furthermore, this study aims to evaluate the in vitro cytotoxic activity of the synthetic compounds against six cancer cell lines, and all the prepared compounds revealed valuable activity compared with the CHS‐828, which is the 2‐[6‐(4‐chlorophenoxy)hexyl]‐1‐cyano‐3‐pyridin‐4‐ylguanidine as the standard drug. Some of the pyrano[2,3‐d]thiazole and thiazolo[4,5‐b]pyridine derivatives showed the highest antitumor activity towards the six cancer cell lines. Moreover, (c‐Met) enzymatic activity of the most potent compounds showed that compounds 3b 2‐(2‐amino‐4,5,6,7 tetrahydrobenzo[b]thiophen‐3‐yl)‐5‐hydroxy‐7‐(2‐hydroxy‐phenyl)‐7H‐pyrano[2,3‐d]thiazole‐6 carbonitrile and 5e 2‐(2‐amino‐4,5,6,7‐tetrahydrobenzo[b]thiophen‐3‐yl)‐5‐hydroxy‐7‐phenyl‐4,7‐dihydrothiazolo[4,5‐b]pyridine‐6‐carbonitrile were with higher activities than foretinib. Three compounds were selected to examine their Pim‐1 kinase where compounds 3b and 7b showed the highest inhibitions. 相似文献
10.
C McConville RM Kalin D Flood 《Rapid communications in mass spectrometry : RCM》1999,13(13):1339-1345
Current methods for stable oxygen isotopic (delta (18)O) analysis of soil water rely on separation of water from the soil matrix before analysis. These separation procedures are not only time consuming and require relatively large samples of soil, but also have been shown to introduce a large potential source of error. Current research at Queen's University Belfast is focused on using direct equilibration of CO(2) with the pore water to eliminate this extraction step using the automated Multiprep system and a Micromass Prism III isotope ratio mass spectrometer (IRMS). The findings of this research indicate the method is less time consuming, more reliable, and reproducible to within accepted limits (+/-0.1% per thousand delta (18)O). In this study the direct equilibration method is used to analyse delta (18)O tracer profiles in the unsaturated zone of field soils, concurrently with chloride tracer profiles, which can be used to assess infiltration rates and mechanisms through the unsaturated zone. Copyright 1999 John Wiley & Sons, Ltd. 相似文献