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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.
The number of trials that is required by an algorithm to produce a given fraction of the problem solutions with a specified level of confidence is analyzed. The analysis indicates that the number of trials required to find a large fraction of the solutions rapidly decreases as the number of solutions obtained on each trial by an algorithm increases. In applications where multiple solutions are sought, this decrease in the number of trials could potentially offset the additional computational cost of algorithms that produce multiple solutions on a single trial. The analysis framework presented is used to compare the efficiency of a homotopy algorithm to that of a Newton method by measuring both the number of trials and the number of calculations required to obtain a specified fraction of the solutions. 相似文献
3.
Humberto Bustos Rodriguez Dagoberto Oyola Lozano Yebrayl A. Rojas Martínez Germán A. Pérez Alcázar Stefan Flege Adam G. Balogh Louis J. Cabri Michael Tubrett 《Hyperfine Interactions》2007,175(1-3):195-206
X-ray diffraction (XRD), Mössbauer spectrometry (MS), secondary ions mass spectroscopy (SIMS) and laser-ablation microprobe–inductively coupled plasma–mass spectrometry (LAM–ICP–MS) were used to study mineral samples of Colombian auriferous ores collected from the “El Diamante” mine, located in the municipality of Guachavez-Nariño, in Colombia. The samples were prepared as polished thin sections and polished sections. From XRD data, quartz, sphalerite and pyrite were detected and their respective cell parameters were estimated. From MS analyses, pyrite, arsenopyrite and chalcopyrite were identified; their respective hyperfine parameters and respective texture were deduced. Multiple regions of approximately 200 × 200 μm in each sample were analyzed with SIMS; the occurrence of “invisible gold” associated mainly with pyrite and secondarily with arsenopyrite could thus be assigned. It was also found that pyrite is of the arsenious type. Spots from 30 to 40 μm in diameter were analyzed with LAM–ICP–MS for pyrite, arsenopyrite and sphalerite; Au is “homogeneously” distributed inside the structure of the arsenious pyrite and the arsenopyrite (not as inclusions); the chemical composition indicates similarities of this “invisible gold”, forming a solid solution with arsenious pyrite and arsenopyrite. One hundred nineteen and 62 ppm of ‘invisible gold’ was quantified in 21 spots analyzed on pyrite and in 14 spots on arsenopyrite, respectively. 相似文献
4.
Robert Andreu Gerard Lligadas Joan Carles Ronda Marina Galià Virginia Cádiz 《Journal of polymer science. Part A, Polymer chemistry》2007,45(21):4965-4973
A new oxazolidine derivative was obtained from phenol, 2‐amino‐2‐methylpropane‐1,3‐diol and paraformaldehyde. The reaction of this novel oxazolidine diol with phenylisocyanate lead to a urethane model compound which can be polymerized thermally by oxazolidine ring opening to give a Mannich bridge structure. Linear segmented polyurethanes were prepared by reaction of different ratios of oxazolidine diol and commercial polyethylenglycol (Mw ~ 400) with 4,4′‐methylenbis (cyclohexylisocyanate) (HMDI, 90% isomers mixture). The polyurethanes were thermally characterized and crosslinked by oxazolidine ring opening to obtain materials which showed improved thermal stability. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4965–4973, 2007 相似文献
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R. Arnaldi R. Averbeck K. Banicz J. Castor B. Chaurand C. Cicalo A. Colla P. Cortese S. Damjanovic A. David A. De Falco A. Devaux A. Drees L. Ducroux H. En’yo A. Ferretti M. Floris A. Foerster P. Force N. Guettet A. Guichard H. Gulkanian J. Heuser M. Keil L. Kluberg J. Lozano C. Lourenço F. Manso A. Masoni P. Martins A. Neves H. Ohnishi C. Oppedisano P. Parracho P. Pillot G. Puddu E. Radermacher P. Ramalhete P. Rosinsky E. Scomparin J. Seixas S. Serci R. Shahoyan P. Sonderegger H.J. Specht R. Tieulent G. Usai R. Veenhof H.K. Wöhri 《The European Physical Journal C - Particles and Fields》2007,49(1):235-241
The NA60 experiment at the CERN SPS has studied low-mass muon pairs in 158 A GeV In–In collisions. A strong excess of pairs
is observed above the yield expected from neutral meson decays. The unprecedented sample size close to 400000 events and the
good mass resolution of about 2% made it possible to isolate the excess by subtraction of the decay sources. The shape of
the resulting mass spectrum shows some non-trivial centrality dependence, but is largely consistent with a dominant contribution
from π+π-→ϱ→μ+μ- annihilation. The associated ϱ spectral function exhibits considerable broadening, but essentially no shift in mass. The
pT-differential mass spectra show the excess to be much stronger at low pT than at high pT. The results are compared to theoretical model predictions; they tend to rule out models linking hadron masses directly to
the chiral condensate.
PACS 25.75.-q; 12.38.Mh; 13.85.Qk 相似文献
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9.
Tomás Pérez-Ruiz Carmen Martínez-Lozano Virginia Tomás Antonio Sanz Jesús Martín 《Fresenius' Journal of Analytical Chemistry》1998,362(4):399-403
A flow-injection configuration is proposed for the fluorimetric determination of ethylenethiourea. The procedure is based
on the inhibitory effect of ethylenethiourea on the oxidation of thiamine to thiochrome by mercury(II). A linear calibration
graph was obtained between 0.1 and 2.0 μg mL–1, with a sampling rate of 40 samples per hour and a relative standard deviation of about 1.11%. The usefulness of the method
was tested for the determination of ethylenethiourea residues in water, milk, potatoes, pear, grape and apple.
Received: 26 January 1998 / Revised: 6 April 1998 / Accepted: 9 April 1998 相似文献
10.
Yu K Singh S Patrito N Chu V 《Langmuir : the ACS journal of surfaces and colloids》2004,20(25):11161-11168
Using cadium oxide (CdO) as the Cd precursor and tri-n-octylphosphine selenide (TOPSe) as the Se source, TOP-capped and TOP/tri-n-octylphosphine oxide (TOPO)-capped CdSe nanocrystals were synthesized without the use of an acid. The synthetic approach involved the addition of a TOPSe/TOP solution into a CdO/TOP solution with or without TOPO at one temperature and subsequent growth at a lower temperature. The temporal evolution of the optical properties, namely, absorption and luminescence, of the growing nanocrystals was monitored in detail. A comprehensive examination on the control of the photoluminescence (PL) properties was performed by systematically varying the TOP/TOPO weight ratio of the reaction media. Surprisingly, a rational choice of 100% TOP or 80% TOP was found to produce "quality" nanocrystals when monitored under the present experimental conditions and growth-time scale. The term "quality" is mainly based on the sharp features and rich substructure exhibited in the absorption spectra of the growing nanocrystals, as well as the sharp features in the emission spectra with narrow full width at half-maximum (fwhm). There are two distinguishable stages of growth: an early stage (<5 min) and a later stage. TOP plays a major role in the control of a slow growth rate in the early stage, while TOPO controls slow growth in the later stage. The optical sensitivity of the growing nanocrystals when dispersed in nonpolar or polar solvents was studied, including two size-dependent parameters, namely, the solvent sensitivity (PL intensity) and nonresonant Stokes shift (NRSS). The insights gained from the present study enable a synthetic approach in which high-quality CdSe nanocrystals are achieved with high synthetic reproducibility. 相似文献