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Szymon Jarzyński Greta Utecht Stanisław Leśniak Michał Rachwalski 《Tetrahedron: Asymmetry》2017,28(12):1774-1779
Enantiomerically pure, chiral secondary and tertiary aziridine alcohols (including the aziridine analogue of ProPhenol—AziPhenol) have proven to be highly effective catalysts for enantioselective asymmetric reactions in the presence of zinc ions, including arylation of aromatic aldehydes, epoxidation of chalcone and addition of diethylzinc to aldehydes, leading to the desired chiral products in high chemical yields (up to 90%) and with ee’s up to 90%. A higher catalytic activity of Prophenol-type bis(aziridine alcohol) in the aforementioned asymmetric transformations has been demonstrated. 相似文献
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Prof. Dr. Sławomir J. Grabowski 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(43):14600-14611
Ab initio calculations were performed on complexes of ZH4+ (Z=N, P, As) and their fluoro derivatives, ZFH3+ and ZF4+, with a HCN (or LiCN) molecule acting as the Lewis base through the nitrogen electronegative center. It was found that the complexes are linked by the Z? H???N hydrogen bond or another type of noncovalent interaction in which the tetravalent heavy atom of the cation acts as the Lewis acid center, that is, when the Z???N link exists, which may be classified as the σ‐hole bond. The formation of the latter interaction is usually preferable to the formation of the corresponding hydrogen bond. The Z???N interaction may be also considered as the preliminary stage of the SN2 reaction. This is supported by the observation that for a short Z???N contact, the corresponding complex geometry coincides with the trigonal‐bipyramidal geometry typical for the transition state of the SN2 reaction. The Z???N interaction for some of complexes analyzed here possesses characteristics typical for covalent bonds. Numerous interrelations between geometrical, topological and energetic parameters are discussed. The natural bond orbital method as well as the Quantum Theory of “Atoms in Molecules” is applied to characterize interactions in the analyzed complexes. The experimental evidences of the existence of these interactions, based on the Cambridge Structure Database search, are also presented. In addition, it is justified that mechanisms of the formation of the Z???N interactions are similar to the processes occurring for the other noncovalent links. The formation of Z???N interaction as well as of other interactions may be explained with the use of the σ‐hole concept. 相似文献
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Pyrroles represent building blocks of conjugated poly(heterocycles) which, as organic conductors, are potential materials for organic electronics. Oxidation of β-substituted pyrroles constitutes an important first step in the process of electropolymerization. Ionization energy and the electron spin density distribution are two the most important properties regarding monomers. These properties are studied as a function of electron-withdrawing and electron-donating substituents of pyrrole ring. Evolution of molecular structure, nature of bonding, and electronic density are studied as an effect of ionization process. 相似文献
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Motzkin numbers are derived from a special case of Random Domino Automaton – recently proposed a slowly driven system being a stochastic toy model of earthquakes. It is also a generalisation of 1D Drossel–Schwabl forest-fire model. A solution of the set of equations describing stationary state of Random Domino Automaton in inverse-power case is presented. A link with Motzkin numbers allows to present explicit form of asymptotic behaviour of the automaton. 相似文献
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Agnieszka Ulanowska Ewa Trawińska Piotr Sawrycki Bogusław Buszewski 《Journal of separation science》2012,35(21):2908-2913
Chemotherapy used as a treatment against lung cancer has influence on metabolic processes occurring in healthy cells. The changes of biochemical pathways proceeded inside cells might be observed in expired air. In the experiment, breath analysis was carried out before and after anticancer therapy. Expired air samples were collected from 22 patients with a biopsy confirmed lung cancer. Volatile organic compounds present in breath were analyzed by gas chromatography/mass spectrometry. For enrichment of analytes solid‐phase microextraction technique was applied. Eight fibers covered by different sorbents were tested. Carboxen‐polydimethylsiloxane fiber revealed the highest extraction efficiency in relation to analytes in breath. The data showed that cytostatic drugs increase the concentration of acetone and isoprene in the breath collected after chemotherapy. Volatile metabolites of administrated drugs were not identified in expired air. 相似文献
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The room temperature 57Fe Mössbauer spectra for binary iron-based solid solutions Fe1???x Ti x , with x in the range 0.010 ≤?x?≤ 0.045, were analysed in terms of binding energy E b between two Ti atoms in the Fe-Ti system. The extrapolated values of E b for x?= 0 were used for computation of enthalpy of solution of titanium in iron. The results were compared with that resulting from the Miedema’s model of alloys as well as those derived from the heat of formation of the system, obtained with both calorimetric measurements and theoretical calculations. The comparison shows that our Mössbauer spectroscopy findings are in a quite good agreement with all the other results mentioned above. 相似文献