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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
2.
Ariel M. Sarotti 《Tetrahedron letters》2004,45(44):8203-8206
A two-step general approach to a new chiral auxiliary starting from levoglucosenone is reported. The compound is obtained by a [4+2] cycloaddition reaction with anthracene followed by a diastereoselective reduction of the C-2 keto function in high overall yield. The auxiliary has been used as chiral template in an asymmetric Diels-Alder reaction of the corresponding acrylic ester derivative with cyclopentadiene and shown to be efficient for asymmetric induction. 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.
5.
Ariel Fernández 《International Journal of Theoretical Physics》1991,30(2):129-136
We establish a mechanism for energy localization in regions of the sugar-phosphate RNA backbone which leads to the formation of transesterification or hydrolysis hot spots. In particular, our results account for the site specificity of the covalent cyclization and cycle reopening in the catalytic intervening sequence (IVS) of a ribosomal RNA. 相似文献
6.
7.
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
8.
In this paper we study the 2-dimension of a finite poset from the topological point of view. We use homotopy theory of finite
topological spaces and the concept of a beat point to improve the classical results on 2-dimension, giving a more complete answer to the problem of all possible 2-dimensions
of an n-point poset.
相似文献
9.
10.
Ariel Fernández 《Theoretical chemistry accounts》1985,67(3):229-233
A structurally stable model of the standard adiabatic gradient field of the potential energy surface for certain pericyclic reactions is derived.These reactions are not subjected to the principles of orbital isomerism or to the Woodward-Hoffmann rules.Use is made of a principle established by Ariel Fernández and Oktay Sinanolu which precludes direct meta-IRC connections between transition states.It is shown that Jahn-Teller isomers of the singlet biradicals involved in the process are not interconvertible since the biradical configuration is not a transition state but a critical point with Hessian matrix with two negative eigenvalues.The topological features of the PES obtained by combinatorial methods are in full agreement with earlier results obtained from MINDO calculations. 相似文献