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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.
Daniel L. Feldheim Del R. Lawson Charles R. Martin 《Journal of Polymer Science.Polymer Physics》1993,31(8):953-957
We report a strong dependence of the thermal stability of Nafion® perfluorosulfonate ionomer on the nature of the counterion associated with the fixed sulfonate site. These results were obtained using thermal gravimetric analysis on a series of alkali metal and alkyl ammonium cation-exchanged Nafion films. We have found that the temperature of decomposition of Nafion is inversely dependent on the size of the exchanged cation; i.e., Nafion films show improved thermal stability as the size of the counter cation decreases. We attribute this inverse relationship of thermal stability with counterion size to an initial decomposition reaction which is strongly influenced by the strength of the sulfonate-coun-terion interaction. © 1993 John Wiley & Sons, Inc. 相似文献
3.
The angular variations of the five-fold differential cross section obtained by using different wave functions of helium are
compared with experimental data. It is found that in the coplanar geometry two kinematical arrangements, (i) equal energy
sharing between the two ejected electrons with one of them ejected along the momentum transfer direction and the other along
varying direction and (ii) the Bethe ridge condition with fixed sum of ejected electron energies and varying angle between
them, are very sensitive to e-e correlations contained in the target wave function. This comparison has been used to show
that open-shell class of wave functions better incorporate e-e correlations than the closed-shell class. 相似文献
4.
Summary We study the integration theory for general integral metrics when restricted to upper integrals q, finding improvements in the relation between the classes of the q-integrable and the ql-integrable functions. We give new results and notions which lead to the desirable characterizations of q-integrable functions as ql-integrable f with q(|f|) < ∞, and of ql-integrable functions via the integrability of their upper truncations, under natural conditions which are fulfilled in most
finitely additive integration theories. 相似文献
5.
V Ravindran Pankaj Agrawal Rahul Basu Satyaki Bhattacharya J Blümlein V Del Duca R Harlander D Kosower Prakash Mathews Anurag Tripathi 《Pramana》2006,67(5):983-992
This is the report of the subgroup QCD of Working Group-4 at WHEPP-9. We present the activities that had taken place in the
subgroup and report some of the partial results arrived at following the discussion at the working group meetings. 相似文献
6.
Flow injection methodology based on sample insertion between two different standard solutions used as carrier streams is described. This approach provides a simple system for continuous recalibration in process control; spectrophotometric and ion-selective electrode procedures are outlined. 相似文献
7.
On the basis of a plane-wave spectrum representation, the polarization features of a transverse quasimonochromatic non-paraxial field have been studied. A relationship has been established between the polarization characteristics in the near field and the coherence and symmetry properties of the beam in the far field. 相似文献
8.
L. Cianchi F. Del Giallo F. Pieralli M. Mancini S. Sciortino G. Spina 《Hyperfine Interactions》1991,66(1-4):387-391
Mössbauer parameters of151Eu in Eu1+x Ba2?x Cu3O7+δ have been studied as a function of temperature, forx=0.15 andx=0.25. The areas of the absorption spectra for the two samples are almost equal. This could mean that thef-Mössbauer factor for151Eu at the barium sites is much smaller than that for151Eu at the rare earth sites, i.e. we only observe the spectra of the latter sites. According to this, the fits of the spectra with a single quadrupolar pattern and with two quadrupolar patterns have given equivalent χ2 values. 相似文献
9.
M. A. Macrì C. Del Gratta L. Di Donato S. Di Luzio G. L. Romani S. Della Penna A. Pasquarelli 《Il Nuovo Cimento D》1994,16(5):425-432
Summary A preliminary study is here reported on a new potential marker for biomagnetic measurements. The marker consists of superparamagnetic
polymer microspheres which were detected in the presence of external steady magnetic fields by means of an r.f.-SQUID magnetometer.
The particles were prepared in samples differing in the concentration value and immersed in a homogeneous magnetic field of
variable intensity. A simple model was taken into account for the distribution of the microspheres in the samples, so that
the theoretical values were compared to the marker field values measured by the biomagnetic sensor. The overall sensitivity
of the experimental apparatus and the minimum concentration value of the marker were then estimated. 相似文献
10.