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1.
Experimental and Theoretical Studies on the Rearrangement of 2‐Oxoazepane α,α‐Amino Acids into 2′‐Oxopiperidine β2,3,3‐Amino Acids: An Example of Intramolecular Catalysis 下载免费PDF全文
Dr. Diego Núñez‐Villanueva Dr. M. Ángeles Bonache Laura Lozano Dr. Lourdes Infantes Prof. José Elguero Prof. Ibon Alkorta Prof. M. Teresa García‐López Dr. Rosario González‐Muñiz Dr. Mercedes Martín‐Martínez 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(6):2489-2500
Enantiopure β‐amino acids represent interesting scaffolds for peptidomimetics, foldamers and bioactive compounds. However, the synthesis of highly substituted analogues is still a major challenge. Herein, we describe the spontaneous rearrangement of 4‐carboxy‐2‐oxoazepane α,α‐amino acids to lead to 2′‐oxopiperidine‐containing β2,3,3‐amino acids, upon basic or acid hydrolysis of the 2‐oxoazepane α,α‐amino acid ester. Under acidic conditions, a totally stereoselective synthetic route has been developed. The reordering process involved the spontaneous breakdown of an amide bond, which typically requires strong conditions, and the formation of a new bond leading to the six‐membered heterocycle. A quantum mechanical study was carried out to obtain insight into the remarkable ease of this rearrangement, which occurs at room temperature, either in solution or upon storage of the 4‐carboxylic acid substituted 2‐oxoazepane derivatives. This theoretical study suggests that the rearrangement process occurs through a concerted mechanism, in which the energy of the transition states can be lowered by the participation of a catalytic water molecule. Interestingly, it also suggested a role for the carboxylic acid at position 4 of the 2‐oxoazepane ring, which facilitates this rearrangement, participating directly in the intramolecular catalysis. 相似文献
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Michael De Castro 《Tetrahedron letters》2004,45(34):6501-6504
2-Deoxy-2-iodo-glycosylamides have been prepared from a variety of protected d-glucals by their reaction with N-iodosuccinimide and amides. Benzyl protected 2-iodoamides, when treated with sodium hydride and 15-crown-5, gave stable C1 N-linked 2-glycooxazolines as the major products. Silyl protected 2-iodoamides afforded the C1 O-linked 2-glycooxazolines; presumably by the rearrangement of unstable N-acylaziridine intermediates. 相似文献
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The oxides A(Ti0.5Te1.5)O6 (A = K, Rb, Cs, Tl), A(Ti0.5W1.5)O6 (A = Rb, Cs, Tl), and Cs(B0.5W1.5)O6 (B = Zr, Hf) have been obtained as polycrystalline powders giving X-ray diffraction patterns characteristic of defect cubic pyrochlores, space group
(No. 227), Z = 8. The best discrepancy R factors, from 0.0265 for Rb(Ti0.5Te1.5)O6 to 0.0554 for Cs(Zr0.5W1.5)O6, were obtained for the B cations randomly distributed at 16(d), A ions at one quarter of 32(e), and oxygen atoms at 48(f) positions. A linear relationship is observed between the a unit cell parameters and the ionic radii of the A cations, as well as the average ionic radii of the B atoms. The results of electrical resistivity measurements for A(Ti0.5Te1.5)O6 (A = K, Rb, Cs, Tl) are given. 相似文献
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Thorsten Brand Kyle Ratinac Jeffrey V. Castro Robert G. Gilbert 《Journal of polymer science. Part A, Polymer chemistry》2004,42(22):5706-5713
A method was developed for free‐radical polymerization in the confines of a hollow latex particle. Hollow particles were prepared via the dynamic swelling method from polystyrene seed and divinylbenzene and had hollows of 500–1000 nm. So that these hollow poly(divinylbenzene) particles could function as submicrometer reactors, the particles were filled with a monomer (N‐isopropylacrylamide) via the dispersion of the dried particles in the molten monomer. The monomer that was not contained in the hollows was removed by washing and gentle abrasion. Free‐radical polymerization was then initiated by γ radiolysis in the solid state. Transmission electron microscopy showed that poly(N‐isopropylacrylamide) formed in the hollow interior of the particles, which functioned as submicrometer reactors. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5706–5713, 2004 相似文献
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A. R. M. Castro M. M. Serna R. N. Faria N. B. Lima 《Journal of magnetism and magnetic materials》2004,280(2-3):273-280
In this study, magnetic domains in Pr16Fe76B8 sintered magnets have been observed by Kerr effect and a histogram of the angular distribution of domain orientations has been used to determine the magnetic texture (cos Φ). The degree of easy-axis alignment of Pr2Fe14B matrix grains in these magnets has been also determined by X-ray pole figure analysis using the (0 0 4) reflection. The (0 0 4) pole figure measurements were carried out by the Schultz's reflection method. The (0 0 4) normalized intensity data has been fitted for a Gaussian distribution and the degree of crystal alignment, cos Θ, has been calculated using the Stoner–Wohlfarth model. Comparison of these methods has been carried out. It has been shown that in magnets with medium and high degrees of crystallographic alignment, the pole figure values are higher than that obtained by the Kerr effect method. Conversely, in magnets with low degrees of alignment, cos Θ is lower than cos Φ. 相似文献
8.
Detection of hepatocarcinoma in rats by integration of the fluorescence spectrum: Experimental model
J. C. Marcassa J. Ferreira S. Zucoloto O. de Castro e Silva Jr. L. G. Marcassa V. S. Bagnato 《Laser Physics》2006,16(5):827-832
The incorporation of spectroscopic techniques into diagnostic procedures may greatly improve the chances for precise diagnostics. One promising technique is fluorescence spectroscopy, which has recently been used to detect many different types of diseases. In this work, we use laser-induced tissue fluorescence to detect hepatocarcinoma in rats using excitation light at wavelengths of 443 and 532 nm. Hepatocarcinoma was induced chemically in Wistar rats. The collected fluorescence spectrum ranges from the excitation wavelength up to 850 nm. A mathematical procedure carried out on the spectrum determines a figure of merit value, which allows the detection of hepatocarcinoma. The figure of merit involves a procedure which evaluates the ratio between the backscattered excitation wavelength and the broad emission fluorescence band. We demonstrate that a normalization allowed by integration of the fluorescence spectra is a simple operation that may allow the detection of hepatocarcinoma. 相似文献
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Beginning with the most general fractal strings/sprays construction recently expounded in the book by Lapidus and Frankenhuysen, it is shown how the complexified extension of El Naschie's cantorian-fractal spacetime model belongs to a very special class of families of fractal strings/sprays whose scaling ratios are given by suitable pinary (pinary, p prime) powers of the Golden Mean. We then proceed to show why the logarithmic periodicity laws in Nature are direct physical consequences of the complex dimensions associated with these fractal strings/sprays. We proceed with a discussion on quasi-crystals with p-adic internal symmetries, von Neumann's Continuous Geometry, the role of wild topology in fractal strings/sprays, the Banach-Tarski paradox, tesselations of the hyperbolic plane, quark confinement and the Mersenne-prime hierarchy of bit-string physics in determining the fundamental physical constants in Nature. 相似文献
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