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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
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Highly Selective Copper‐Catalyzed Asymmetric [3+2] Cycloaddition of Azomethine Ylides with Acyclic 1,3‐Dienes
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María González‐Esguevillas Ana Pascual‐Escudero Dr. Javier Adrio Prof. Dr. Juan C. Carretero 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(12):4561-4565
The first examples of the catalytic asymmetric 1,3‐dipolar cycloaddition of azomethine ylides with acyclic activated 1,3‐dienes (and 1,3‐enynes) are described. Under copper catalysis, a selective cycloaddition at the terminal γ,δ‐C?C bond is observed. In addition, depending on the ligand used, either the exo or the endo adduct can be obtained with high selectivity. Under appropriate reaction conditions, the acyclic 1,6‐addition product is detected, suggesting a stepwise mechanism. The resulting C4‐alkenyl‐substituted pyrrolidines are suitable substrates for further access to polycyclic systems, as highlighted by the preparation of hexahydrochromeno[4,3‐b]pyrrole and the tetracyclic core of the alkaloid gracilamine. 相似文献
6.
D. De Salvador A. Coati E. Napolitani M. Berti A.V. Drigo M.S. Carroll J.C. Sturm J. Stangl G. Bauer L. Lazzarini 《Applied Physics A: Materials Science & Processing》2002,75(6):667-672
In this work we investigate the diffusion and precipitation of supersaturated substitutional carbon in 200-nm-thick SiGeC
layers buried under a silicon cap layer of 40 nm. The samples were annealed in either inert (N2) or oxidizing (O2) ambient at 850 °C for times ranging from 2 to 10 h. The silicon self-interstitial (I) flux coming from the surface under
oxidation enhances the C diffusion with respect to the N2-annealed samples. In the early stages of the oxidation process, the loss of C from the SiGeC layer by diffusion across the
layer/cap interface dominates. This phenomenon saturates after an initial period (2–4 h), which depends on the C concentration.
This saturation is due to the formation and growth of C-containing precipitates that are promoted by the I injection and act
as a sink for mobile C atoms. The influence of carbon concentration on the competition between precipitation and diffusion
is discussed.
Received: 19 October 2001 / Accepted: 19 December 2001 / Published online: 20 March 2002 / Published online: 20 March 2002 相似文献
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Lithium (10–150 ng ml?1) in wine is determined by atomic absorption spectrometry by direct nebulization and after digestion with mixed acids. The results of methods are similar. Thirty-four wines from various Spanish provinces are analysed. 相似文献
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P. González D. Fernández J. Pou E. García J. Serra B. León M. Pérez-Amor T. Szörényi 《Applied Physics A: Materials Science & Processing》1993,57(2):181-185
A study of the gas-phase parameters involved in ArF laser induced chemical vapour deposition of silicon-oxide thin films is presented. A complete set of experiments has been performed showing the influence of the concentration of the precursor gases, N2O and SiH4, and their influence on total and partial pressures on film growth and properties. In this paper we demonstrate the ability of this LCVD method to deposit silicon oxide films of different compositions and densities by appropriate control of gas composition and total pressure. Moreover, a material specific calibration plot comprising data obtained using different preparation techniques is presented, allowing determination of the stoichiometry of SiO
x
films by using FTIR spectroscopy independently of the deposition method. For the range of processing conditions examined, the experimental results suggest that chemical processes governing deposition take place mainly in the gas phase. 相似文献
9.
Salvador Hernández 《Topology and its Applications》2007,154(10):2089-2098
Let C(X,G) be the group of continuous functions from a topological space X into a topological group G with pointwise multiplication as the composition law, endowed with the uniform convergence topology. To what extent does the group structure of C(X,G) determine the topology of X? More generally, when does the existence of a group homomorphism H between the groups C(X,G) and C(Y,G) implies that there is a continuous map h of Y into X such that H is canonically represented by h? We prove that, for any topological group G and compact spaces X and Y, every non-vanishing C-isomorphism (defined below) H of C(X,G) into C(Y,G) is automatically continuous and can be canonically represented by a continuous map h of Y into X. Some applications to specific groups and examples are given in the paper. 相似文献
10.
Automatic detection and identification of shocks in Gaussian state‐space models: a Bayesian approach
An automatic monitoring and intervention algorithm that permits the supervision of very general aspects in an univariate linear Gaussian state–space model is proposed. The algorithm makes use of a model comparison and selection approach within a Bayesian framework. In addition, this algorithm incorporates the possibility of eliminating earlier interventions when subsequent evidence against them comes to light. Finally, the procedure is illustrated with two empirical examples taken from the literature. Copyright © 2005 John Wiley & Sons, Ltd. 相似文献