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71.
Albrecht Ł Ransborg LK Gschwend B Jørgensen KA 《Journal of the American Chemical Society》2010,132(50):17886-17893
The first enantioselective methodology for the synthesis of electron-poor 2-hydroxyalkyl- and 2-aminoalkyl furanes is demonstrated in this study. It utilizes a highly stereoselective organocatalytic one-pot reaction cascade: epoxidation or aziridination of α,β-unsaturated aldehydes followed by Feist-Be?nary reaction of various 1,3-dicarbonyl compounds to give the target furanes. This efficient multibond forming reaction cascade benefits from low catalyst loadings and readily available starting materials. Furthermore, the possibility to interrupt the reaction sequence at the stage of the corresponding optically active 2-hydroxyalkyl- and 2-aminoalkyl 2,3-dihydrofuranes with three stereogenic centers is also presented. Finally, models which account for the formation of the optically active 2,3-dihydrofuranes are proposed. 相似文献
72.
Angelika Baranowska Krzysztof Z. Ła̧czkowski Andrzej J. Sadlej 《Journal of computational chemistry》2010,31(6):1176-1181
We have carried out extensive studies on the basis set dependence of the calculated specific optical rotation (OR) in molecules at the level of the time–dependent Hartree–Fock and density functional approximations. To reach the limits of the basis set saturation, we have devised an artificial model, the asymmetrically deformed (chiral) methane (CM) molecule. This small system permits to use basis sets which are prohibitively large for real chiral molecules and yet shows all the important features of the basis set dependence of the OR values. The convergence of the OR has been studied with n‐aug‐cc‐pVXZ basis sets of Dunning up to the 6–ζ. In a parallel series of calculations, we have used the recently developed large polarized (LPolX) basis sets. The relatively small LPolX sets have been shown to be competitive to very large n‐aug‐cc‐pVXZ basis sets. The conclusions reached in calculations of OR in CM concerning the usefulness of LPolX basis sets have been further tested on (S)‐methyloxirane and (S)‐fluoro‐oxirane. The smallest set of the LPolX family (LPol–ds) has been found to yield OR values of similar quality as those obtained with much larger Dunning's aug‐cc‐pVQZ basis set. These results have encouraged us to carry out the OR calculations with LPol–ds basis sets for systems as large as β‐pinene and trans‐pinane. In both cases, our calculations have lead to the correct sign of the OR value in these molecules. This makes the relatively small LPol–ds basis sets likely to be useful in OR calculations for large molecules. © 2009 Wiley Periodicals, Inc. J Comput Chem, 2010 相似文献
73.
We show that the equality m1(f(x))=m2(g(x)) for x in a neighborhood of a point a remains valid for all x provided that f and g are open holomorphic maps, f(a)=g(a)=0 and m1,m2 are Minkowski functionals of bounded balanced domains. Moreover, a polynomial relation between f and g is obtained. 相似文献
74.
75.
Łukasz Dębowski 《Journal of Theoretical Probability》2014,27(2):539-551
We investigate stationary hidden Markov processes for which mutual information between the past and the future is infinite. It is assumed that the number of observable states is finite and the number of hidden states is countably infinite. Under this assumption, we show that the block mutual information of a hidden Markov process is upper bounded by a power law determined by the tail index of the hidden state distribution. Moreover, we exhibit three examples of processes. The first example, considered previously, is nonergodic and the mutual information between the blocks is bounded by the logarithm of the block length. The second example is also nonergodic but the mutual information between the blocks obeys a power law. The third example obeys the power law and is ergodic. 相似文献
76.
Łukasz Janczewski Małgorzata Walczak Justyna Frączyk Zbigniew J. Kamiński 《合成通讯》2013,43(23):3290-3300
The microwave-assisted Cannizzaro reaction was studied in order to develop fully reproducible synthetic protocols for transformation of aldehydes to carboxylic acid and alcohols. Optimised were the following process parameters: power, temperature, and time. Aromatic, heteroaromatic and aliphatic aldehydes were used in the studies. It was found that furfural, thiophene-2-carbaldehyde, pyridinecarboxaldehyde and aromatic aldehydes react under mild conditions, while 1-methyl-pyrrole-2-carboxaldehyde derivatives and aliphatic aldehydes require more drastic reaction conditions and a longer exposure time to microwave radiation. 相似文献
77.
Sajewicz Mieczysław Wojtal Łukasz Hajnos Michał Waksmundzka-Hajnos Monika Kowalska Teresa 《平面色谱法杂志一现代薄层色谱法》2010,23(4):270-276
JPC – Journal of Planar Chromatography – Modern TLC - In a previous paper we discussed the possibility of fractionating the essential oils of different sage species by low-temperature... 相似文献
78.
In this paper, the numerical modelling of the flow through the low‐pressure steam turbine last stage was presented. On the basis of predicted wet steam flow‐field, the aerodynamic as well as thermodynamic losses were estimated. For calculations of the wet steam steady flow‐field three numerical methods were employed. The first method was a streamline curvature method (SCM). The commercial CFD code (CFX‐TACflow) and an in‐house code, both solving the 3‐D RANS equations, were the next two methods. In the wet steam region, by means of all three methods, the equilibrium flow was modelled. Additionally, the in‐house CFD code was used for modelling of the non‐equilibrium steam condensing flow. In this work, the comparison of the cascade loss coefficient for stator and rotor and selected flow parameters for the stage were presented, compared and discussed. Copyright © 2006 John Wiley & Sons, Ltd. 相似文献
79.
Zbigniew Grobelny Barbara Morejko-Bu? Adalbert Maercker 《European Polymer Journal》2004,40(2):409-414
Transfer of one electron from potassium anion of alkalide K−, K+(15-crown-5)2 to the double bond of vinyloxirane results in the oxirane ring opening exclusively in the α-position. K0 and radical anions are formed in the process. The former transfers the second electron mainly to the next monomer molecule. The latter dimerize to potassium glycoxides, which initiate the polymerization of vinyloxirane. The introduction of two CH2 groups between the double bond and the oxirane ring changes the way of electron transfer. The oxirane ring of 3-butenyloxirane becomes the electron acceptor and its opening occurs in the β-position. In this case K0 transfers the second electron to the primarily formed radical anion giving an organopotassium intermediate. It reacts with crown ether. Potassium alkoxides are the reaction products. They become the real initiators of 3-butenyloxirane polymerization. 相似文献
80.
L. Łukaszuk 《Zeitschrift fur Physik C Particles and Fields》1991,50(1):133-138
We perform summation of ladder diagrams in the high energy, large momentum limit. This leads to new results for both perturbative and non-perturbative approaches. In particular, an explicit expression for any diagram's contribution is given, the non-perturbative form of asymptotically non-analytic terms is found and representation of amplitude as a series of Regge poles is presented.Supported in part by Polish Ministery of National Education, grant no. CPBP 01.03 相似文献