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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.
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
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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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6.
MM. J. Duflos D. Letouz G. Queguiner P. Pastour 《Journal of heterocyclic chemistry》1973,10(6):1083-1084
This communication describes the synthesis of l-methyl-2,3-diformylpyrrole. This new compound is used to prepare a new heterocycle, l-methylcyclohepta[b]pyrrol-6-one and thus allows a new synthesis of l-methylpyrrolo[2,3-d]pyridazine. 相似文献
7.
E. Ferrero J. F. Espeso J. G. de la Campa J. de Abajo A. E. Lozano 《Journal of polymer science. Part A, Polymer chemistry》2002,40(21):3711-3724
A series of polyisophthalamides containing pendent phthalimido groups and flexible side spacers were prepared from four novel diacids and three commercial aromatic diamines. These polyamides were prepared in high yields and with high molecular weights by direct polycondensation with triphenyl phosphite and pyridine as condensing agents. The weight‐average and number‐average molecular weights, measured by gel permeation chromatography, were 70,000–137,000 and 47,000–86,000 g/mol, respectively. The novel polyamides were amorphous and readily soluble and showed glass‐transition temperatures of 150–240 °C, as measured by differential scanning calorimetry. Thermogravimetric analysis showed that the 10% weight‐loss temperatures in nitrogen were 355–430 °C, a significant improvement in thermal stability having been observed with the increase in the side‐chain length. A theoretical quantum mechanical study was successfully carried out to explain these results. Flexible and tough films, cast from polymer solutions, showed tensile strengths of 50–125 MPa. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3711–3724, 2002 相似文献
8.
Purified frog epidermis tyrosinase was immobilized on the following supports: CNBr-Sepharose 4B, Enzacryl AA, Enzacryl AH, Enzacryl Polythiolactone, and Enzacryl Polyacetal. The enzyme was active on all supports except when Enzacryl Polyacetal was used. The stability increased on immobilization. Enzacryl AA was the best support assayed. The Enzacryl AA-enzyme complex was 30- to 40-fold more stable to inactivation reaction than soluble enzyme, and maintained its activity when stored and assayed repeatedly. The immobilized enzyme on the other supports was also more stable than the soluble form. The pH-activity profile, thermal stability, storage stability, and the effect of protein concentration on activity of the immobilized enzyme have been studied. The properties observed for the immobilized enzyme were different than those of the soluble enzyme. The main reason for this difference could be due to enzyme modification through tyrosine groups of the enzyme; to conformational changes produced in the union to the matrix; and to microenvironmental differences created by the matrix. 相似文献
9.
García Falcón S González Amigo S Lage Yusty MA López de Alda Villaizán MJ Simal Lozano J 《Talanta》1996,43(4):659-664
We have developed a simple, rapid, inexpensive method for the determination of benzo[a]pyrene (BP, a known carcinogen) in smoking-flavour agents (water-soluble liquid smoke; WSLS). After purification of the WSLS by a single passage through a Sep Pak C18 Plus cartridge, BP in the hexane eluate was determined by second derivative constant-wavelength synchronous spectrofluorimetry. Method precision (RSD < 6%) and recovery ( approximately 92%) were satisfactory, and the detection and quantification limits (1.05 and 2.28 mug kg(-1) respectively) indicated that the current maximum permissible concentration of BP in smoke flavourings (10 mug kg(-1)) can be monitored by this method. 相似文献
10.