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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
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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
2.
Palladium-containing zeolites catalyze the cycloisomerization of diethyl diallylmalonate to dimethylcyclopentenes. When the reaction is carried out in toluene, the performance of the palladium catalyst depends on the pore size of the zeolites. At 60 °C, palladium adsorbed on large pore size Beta zeolite (pore size ∼7.4 Å) is more active than medium pore size ZSM-5 (pore size ∼5.4 Å). This lower activity of ZSM-5 compared to Beta is attributable to the restricted diffusion of reagent and products through the ZSM-5 channels as compared to Beta zeolite. However, due to the gas-like diffusion characteristic of the supercritical state, the activity of ZSM-5 increases and becomes identical to that of Beta zeolite using supercritical CO2 as medium. 相似文献
3.
4.
Despite the large cost of bodily injury (BI) claims in motor insurance, relatively little research has been done in this area. Many companies estimate (and therefore reserve) bodily injury compensation directly from initial medical reports. This practice may underestimate the final cost, because the severity is often assessed during the recovery period. Since the evaluation of this severity is often only qualitative, in this paper we apply an ordered multiple choice model at different moments in the life of a claim reported to an insurance company. We assume that the information available to the insurer does not flow continuously, because it is obtained at different stages. Using a real data set, we show that the application of sequential ordered logit models leads to a significant improvement in the prediction of the BI severity level, compared to the subjective classification that is used in practice. We also show that these results could improve the insurer’s reserves notably. 相似文献
5.
Karla J. Moreno Miroslaw Maczka Ulises Amador 《Journal of solid state chemistry》2006,179(12):3805-3813
The structural and microstructural characteristics of metastable Gd2(Ti1−yZry)2O7 powders prepared by mechanical milling have been studied by a combination of XRD and Raman spectroscopy. Irrespective of their Zr content, as-prepared powder phases present an anion-deficient fluorite-type of structure as opposed to the pyrochlore equilibrium configuration obtained for the same solid solution by other synthetic routes. These fluorites are stable versus thermal activation, at least up to temperatures of 800 °C. For the Ti-rich compositions, thermal treatments at higher temperatures facilitate the rearrangement of the cation and anion substructures and the relaxation of mechanochemically induced defects whereas for compositions with high Zr content, the fluorite crystal structure is retained even at temperatures as high as 1200 °C. Interestingly enough, transient pyrochlores showing a very unusual cation distribution were observed during the thermally induced defect-recovery process. 相似文献
6.
José A. Anquela Teresa Cortés Miguel Gómez-Lozano Mercedes Siles-Molina 《Acta Mathematica Hungarica》2004,103(3):177-196
We investigate the basic properties of the different socles that can be considered in not necessarily semiprime associative
systems. Among other things, we show that the socle defined as the sum of minimal (or minimal and trivial) inner ideals is
always an ideal. When trivial inner ideals are included, this inner socle contains the socles defined in terms of minimal
left or right ideals.
This revised version was published online in June 2006 with corrections to the Cover Date. 相似文献
7.
Joaquin Barbera Anne-Marie Levelut Mercedes Marcos Pilar Romero Jose Luis Serrano 《Liquid crystals》1991,10(1):119-126
We present a comparative study of various metallomesogenic complexes, using X-ray diffraction methods. For a given ligand linked to different metal atoms (Cu, Ni, VO), the nature of this central atom influences mainly the magnetic susceptibilities of the mesophases. With different ligands, which keep the close neighbourhood of the metal atom unchanged, the apparent length of the mesogenic unit is longer for short ligands than for longer ones. This unexpected behaviour is qualitatively well explained by taking into account the global shape of the different complexes. 相似文献
8.
Rafael Caballero Mercedes González Flor M Guerrero Julián Molina Concepción Paralera 《European Journal of Operational Research》2007
In this work we present a multiobjective location routing problem and solve it with a multiobjective metaheuristic procedure. In this type of problem, we have to locate some plants within a set of possible locations to meet the demands of a number of clients with multiple objectives. This type of model is used to solve a problem with real data in the region of Andalusia (Spain). Thus, we study the location of two incineration plants for the disposal of solid animal waste from some preestablished locations in Andalusia, and design the routes to serve the different slaughterhouses in this region. This must be done while taking into account certain economic objectives (start-up, maintenance, and transport costs) and social objectives (social rejection by towns on the truck routes, maximum risk as an equity criterion, and the negative implications for towns close to the plant). 相似文献
9.
10.
Ignacio Moreno Pablo Velásquez Daniel Puerto Asticio Vargas 《Optics Communications》2006,260(1):12-18
In this work, we show a very simple birefringent filter useful to modulate a broadband light spectrum. We first show the generation of various oscillating spectra using two identical multiple-order waveplates. In particular a sinusoidal broadband spectrum with a rapid oscillation is obtained. This spectrum is amplitude modulated by adding another waveplate to the system. This waveplate has a small phase shift, and with the proper orientation generates amplitude beats on the broadband spectrum. Finally, we show how this system can be voltage controlled by means of a ferroelectric liquid crystal modulator. We experimentally demonstrate this behavior with the aid of a portable spectrophotometer, and we provide a theoretical explanation on the basis of the Jones matrix formalism. 相似文献