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排序方式: 共有362条查询结果,搜索用时 15 毫秒
101.
Pizzonero M Keller L Dumas F Ourevitch M Morgant G Spasojević-de Biré A Bogdanović G Ghermani NE D'Angelo J 《The Journal of organic chemistry》2004,69(13):4336-4350
In connection with a total synthesis of cephalotaxine (1a), we have examined the addition of various nucleophilic reagents to [ABC] subunits 2 and 7 possessing a pyrrolobenzazepine core. In fact, this reaction implicates invariably the carbonyl group of 2. Regarding the reaction of 7 with nucleophiles, the most striking aspect is the complete lack of reactivity of the enaminonitrile moiety. For instance, the condensation of 7 with methylmagnesium bromide involves exclusively the cleavage of the dioxole ring, yielding regioisomers 9 and 10. With the aim of understanding the unexpected reactivity of 2 and 7 toward nucleophiles, crystallographic studies of 2 and 7 and an experimental electron density determination of 7 were carried out. The marked reactivity of the carbonyl group of 2 was interpreted by invoking the weakness of the amide resonance, due to a pronounced delocalization of the N(9) lone pair over the enaminonitrile moiety. The electron density study of 7 reveals this electron delocalization along the enaminonitrile fragment, highlighted and quantified through the bond geometries, topological indicators, and atomic charges, a phenomenon that is responsible for the failure of the addition of nucleophilic species. 相似文献
102.
The limiting swelling of a polyurethane of well defined structure was investigated in numerous solvents. It was found that the polymer dissolved for a very narrow range of solubility parameter (δ) values. The swelling in various solvent mixtures exhibits a sharp maximum for δ = 9.6±0.2. This value is suggested for δ of the polyurethane. Theoretical evaluations lead to a similar result. It was also found that for N-vinylpyrrolidone, a solvent for the polyurethane, δ is between 9.5 and 11.1. 相似文献
103.
Ladame S Fauré R Denier C Lakhdar-Ghazal F Willson M 《Organic & biomolecular chemistry》2005,3(11):2070-2072
A new series of "bi-substrate" analogues have been synthesized as potential inhibitors of the glyceraldehyde-3-phosphate dehydrogenase and one lead compound has been identified that inhibits the enzyme from Trypanosoma cruzi with good affinity and very high (50-fold) specificity. 相似文献
104.
Salom-Roig XJ Hamzé A Calas M Vial HJ 《Combinatorial chemistry & high throughput screening》2005,8(1):49-62
A new antimalarial pharmacological approach based on inhibition of the plasmodial phospholipid metabolism has been developed. The drugs mimic choline structure and inhibit de novo phosphatidylcholine biosynthesis. Three generations of compounds were rationally designed. Bisquaternary ammonium salts showed powerful antimalarial activity, with IC(50) in the nanomolar range. To remedy their low per os absorption, bioisosteric analogues (bis-amidines) were designed and exhibited similar powerful activities. Finally, the third generation compounds are bis-thiazolium salts and their non-ionic precursors: prodrugs, which in vivo can lead to thiazolium drugs after enzymatic transformation. The compounds are equally effective against multiresistant Plasmodium falciparum malaria. These molecules exert a very rapid cytotoxic effect against malarial parasites in the very low nanomolar range and are active in vivo against P. vinckei-infected mice, with ED(50) lower than 0.2 mg/kg. They are able to cure highly infected mice and, retain full activity after a single injection. They also retain full activity against P. falciparum and P. cynomolgi in primate models with no recrudescence and at lower doses. Compounds are accumulated in P.falciparum-infected erythrocyte, which ensures their potency and specificity. Recently, we discovered that compounds also interact with malarial pigment enhancing the antimalarial effect. It is quite likely that they are dual molecules, exerting their antimalarial activity via two simultaneous toxic effects on the intracellular intraerythrocytic parasites. The current leader compounds are accessible in few steps from commercial products. These crystalline molecules present a remarkable biological activity and low toxicity which is promising for the development of a new antimalarial drug. 相似文献
105.
Michèle Giacomini Bernard Pullman Bernard Maigret 《Theoretical chemistry accounts》1970,19(4):347-364
Résumé La méthode des orbitales moléculaires dans la forme PCILO est utilisée pour l'étude des cartes conformationnelles du maltose, de la cellobiose et du sucrose. Le calcul est effectué en deux étapes. Dans la première les conformations des cycles pyranosiques et furunosiques sont figées et les seules variables sont constituées par les angles et du pont glycosidique. Dans la seconde on tient compte également des angles correspondant aux rotations possibles des OH proches de la liaison glycosidique. Les résultats du calcul quantique sont comparés avec ceux des calculs empiriques et, dans la mesure du possible, avec ceux de l'expérience.
Quantum mechanics applied to conformational studies of disaccharides
The molecular orbital method in the PCILO approximation is used for the determination of the conformational maps of maltose, cellobiose and sucrose. The calculations are carried out in two steps. In the first one, the conformation of the pyranose and furanose rings is fixed and the only variables are the angles and of rotations around the glycosidic linkages. In the second, rotations of the OH groups in the vicinity of the glycosidic bond are included in the computations. The results of the quantum-mechanical calculations are compared with those of previous empirical ones and with the available experimental evidence.
Zusammenfassung Die MO-Methode in der PCILO-Näherung wird zur Bestimmung der Konformationskarten von Maltose, Cellobiose und Saccharose verwendet. Die Berechnungen werden in zwei Stufen ausgeführt. In der ersten wird die Konformation des Pyranose- und des Furanose-Ringes festgehalten und die einzigen Variablen sind die Winkel und der Rotation um die Glykosid-Bindungen. In der zweiten Stufe werden die Rotationen der OH-Gruppen in der Nachbarschaft der Glykosid-Bindung bei der Berechnung mit berücksichtigt. Die Ergebnisse der quantenmechanischen Berechnungen werden mit denjenigen früherer empirischer Berechnungen sowie den experimentellen Ergebnissen — soweit möglich — verglichen.相似文献
106.
Cristau P Temal-Laïb T Bois-Choussy M Martin MT Vors JP Zhu J 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(9):2668-2679
A unified strategy for the synthesis of mauritines A (5), B (6), C (7), and F (10) has been developed based on a key intramolecular nucleophilic aromatic substitution reaction (S(N)Ar) for the formation of the strained 14-membered paracyclophane. It was demonstrated that the outcome of the cycloetherification is independent of the stereochemistry of the peptide backbone and that both (1R)-16 and (1S)-16 cyclized smoothly to provide the corresponding macrocycle. On the other hand, dehydration of the secondary benzylic alcohol, via the phenylselenide intermediate, is configuration dependent. (1R)-25 underwent the two-step syn-elimination much more easily than (1S)-22. A modified reductive deamination procedure via the diazonium intermediate was developed. A complete assignment of proton and carbon NMR spectroscopy signals for these natural products is reported for the first time. 相似文献
107.
Methods for the synthesis of dihydroazaphenanthrene fused to macrocycles (2) and medium-ring heterocycles (4), as well as 1,4-benzodiazepine-2,5-diones (5), are developed. A distinctly different catalytic property of palladium and copper catalysts was uncovered that leads to the development of a divergent synthesis of two different heterocyclic scaffolds from the same starting materials, simply by metal-switching. Thus, starting from linear amide 3, palladium acetate triggers a domino intramolecular N-arylation/C-H activation/aryl-aryl bond-forming process to provide 4, while copper iodide promotes only the intramolecular N-arylation reaction leading to 5. In combination with the Ugi multicomponent reaction (Ugi-4CR) for the preparation of the linear amides, a two-step synthesis of either the 5,6-dihydro-8H-5,7a-diazacyclohepta[jk]phenanthrene-4,7-dione (4) or 1,4-benzodiazepine-2,5-diones (5), by appropriate choice of metal catalyst, is subsequently developed from very simple starting materials. 相似文献
108.
Erwin Buncel Michèle Decouzon Alessandra Formento Jean-François Gal Marta Herreros Lewyn Li Pierre-Charles Maria Ilmar Koppel Riho Kurg 《Journal of the American Society for Mass Spectrometry》1997,8(3):262-269
The kinetic method was used for the quantitative determination of lithium-cation affinities by Fourier transform ion cyclotron resonance. This method was applied to a series of XYSO and XYSO2 compounds. Proton basicities of the SO and SO2 compounds were also determined. When comparison is made between Li+ basicities and proton basicities, a linear regression encompassing XYSO and XYSO2 families suggests that Li+ may be bonded in a similar way to the SO and SO2 moieties, that is, to only one oxygen on the latter. PM3 calculations support this hypothesis. 相似文献
109.
Busnel O Bi L Dali H Cheguillaume A Chevance S Bondon A Muller S Baudy-Floc'h M 《The Journal of organic chemistry》2005,70(26):10701-10708
[structure: see text] A solid-phase fluorenylmethyloxycarbonyl (Fmoc)-based synthesis strategy is described for "mixed" aza-beta3-peptides as well as a convenient general approach for their required building blocks, the aza-beta3-amino acid residues (aza-beta3-aa). These monomers allow the synthesis of relatively large quantities of pure mixed aza-beta3-peptides. The required Fmoc-substituted aza-beta3-amino acids are accessible by convenient synthesis, and a number of monomers including those containing side chains with functional groups have been synthesized. The method was applied toward the solid-phase synthesis of aza-beta3-peptide mimetics of a biologically active histone H4 sequence. 相似文献
110.
The characterisation of the physical state of frozen and freeze dried biological products delivers powerful information for freeze-drying process optimisation. The influence of lactic acid bacterial cell size, shape and concentration on collapse temperature of concentrated bacterial suspensions was investigated. Lactobacillus bulgaricus (long rods), and Streptococcus thermophilus (small spherical cells) were used as cellular models for this study. Whatever the strain, when lactic acid bacterial cells were added to protective solutions, the collapse temperature increased, thus allowing the use of higher sublimation temperatures during primary drying than expected from the protective medium alone. Moreover, the higher the cell concentration, the greater the effect, linear relationships existing between the collapse temperatures and the total dried matter. Cells of both strains gave a kind of robustness to the freeze-dried product, but the increase observed in collapse temperature was considerably higher (3 - 5 degree C) for L. bulgaricus compared to S. thermophilus. This result was ascribed to the different size and shape of the strains. 相似文献