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51.
Despite the popularity of boron and silicon allylation reagents in stereocontrolled synthesis, they suffer from a number of inherent limitations that have slowed down their development as synthetic tools for nucleophilic additions to carbonyl compounds and imine derivatives. These limitations are the low reactivity and diastereoselectivity of allyl trialkylsilane reagents, and the lack of catalytic systems for the activation and substoichiometric control of enantioselectivity in the additions of allyl boron reagents. To develop more efficient and general methods for the control of absolute stereochemistry in the resulting homoallylic alcohols, new approaches aimed at solving the problem of activation of allylic boron and silicon reagents are needed. This Minireview describes a number of recent approaches that have been devised to address this problem. 相似文献
52.
Density functional theory (PBE and B3LYP) was used to study asymmetric hydrogenations of alkenes catalyzed by an iridium imidazolylidine oxazoline complex. The calculation predicts that the alkene preferentially coordinates to the site trans to the carbene. The coordinated alkene then reacts first with the H2 ligand, then with the hydride to form alkane. Finally, the alkane is released by equilibrating with extrinsic H2 and alkene. Enantioface selectivities for hydrogenations of trisubstituted alkenes seem to be driven primarily by steric interactions with the adamantyl part of the ligand; only the smallest substituents can adopt a site close to it. Application of this theoretical model leads to correct predictions regarding the experimentally observed sense and magnitude of the enantioselectivities. 相似文献
53.
The approximation of electron densities 总被引:1,自引:0,他引:1
This paper discusses the approximate representation of the electron density produced by an ab initio calculation. A linear combination of Gaussians is fitted to the density by minimizing a functional which is the consequent error in field-energy. The practical implementation of the procedure, following a Gaussian 80 calculation, is described and some of the complications are analysed. 相似文献
54.
An algebraic method that includes Gibbs minimization for performing phase equilibrium calculations for any number of components or phases 总被引:1,自引:0,他引:1
Gustavo A. Iglesias-Silva Adrin Bonilla-Petriciolet Philip T. Eubank James C. Holste Kenneth R. Hall 《Fluid Phase Equilibria》2003,210(2):229-245
The most widely used technique for performing phase equilibria calculations is the K-value method (equality of chemical potentials). This paper proposes a more efficient algorithm to achieve the results that includes Gibbs minimization when we know the number of phases. Using the orthogonal derivatives, the tangent plane equation and mass balances, it is possible to reduce the Gibbs minimization procedure to the task of finding the solution of a system of non-linear equations. Such an operation is easier and faster than finding tangents or areas, and appears to converge as fast as the K-value method. Examples illustrate application of the new technique to two and three phases in equilibrium for binary and ternary mixtures. 相似文献
55.
Mohammad A. Khadim Lawrence D. Colebrook Laurance D. Hall 《Journal of heterocyclic chemistry》1980,17(4):651-656
Proton spin-lattice relaxation rates (R1 values) have been measured, at 270 MHz, for a series of N-aryl isoindolinones. A normalization procedure has been used to enable comparison of R1 values in different compounds by minimizing the effects on relaxation rates of changes in motional correlation times accompanying changes in substitution patterns. A substantial (4.3-fold) dynamic range of R1 values has been observed, and individual values have been correlated with the molecular environments of the nuclei. There is evidence for an interring relaxation process. 相似文献
56.
The electrical resistivity and Hall coefficient of Zn3P2 have been measured for single crystal and thin polycrystalline film samples which were annealed over a range of equilibrium vapor compositions and temperatures. The room temperature electrical resistivity of single crystal samples annealed at 573 K varied from approximately 105Ω-cm for single crystals heated in equilibrium with zinc to 10 Ω-cm for those annealed in a phosphorus rich ambient. Hall measurements indicate that a variation in carrier concentration is responsible for these changes. The experimentally observed dependence of carrier concentration [h° ], (cm?3) on phosphorus pressure is given by [h°] = 1.32 · 1016 [p(P4)]0.13 for samples annealed at 573 K. The experimentally determined pressure dependence is in good agreement with a model based on phosphorus interstitials acting as acceptors. The pressure and temperature dependence of the carrier concentration yield the equilibrium constant KI for the formation of interstitial phosphorus defects according to the reaction where . The accommodation of phosphorus interstitials is discussed in light of the crystal structure of Zn3P2. 相似文献
57.
58.
The use of stable carbon isotope analysis to detect the abuse of testosterone in cattle. 总被引:3,自引:0,他引:3
The use of stable carbon isotope analysis to detect the administration of anabolic steroids to cattle was investigated. Samples were extracted by solid-phase extraction on C18 cartridges. Stable isotope ratios (13C:12C) were measured by gas chromatography-isotope ratio mass spectrometry (GC-IRMS) of the underivatised extracts. A programmed temperature vaporiser (PTV) injector was installed in the GC-IRMS system, which conferred a number of advantages. First, it allowed large volumes of sample to be injected whilst the injector liner was cool. The solvent was subsequently vented to the atmosphere prior to transfer of the sample to the GC column. Thus a significantly greater amount of sample could be presented for analysis, thereby increasing the sensitivity. Second, by this means virtually all the solvent could be removed prior to analysis. This eliminates solvent peak tailing, which can be a major problem in GC-IRMS. Finally, the PTV allowed the use of higher initial GC oven temperatures, which in turn facilitated the analysis of underivatised steroids by reducing the GC run time and improving the chromatographic peak shape. The carbon isotope composition of 5 beta-androstane-3 alpha,17 alpha-diol, the major metabolite of testosterone found in bovine bile, was measured in bile samples from untreated cattle and from cattle injected intramuscularly with testosterone or a mixture of testosterone esters. There was considerable inter-animal variation in the values obtained and there was no significant difference between samples from treated and untreated animals. However, when the isotopic composition of the metabolite was normalised with respect to that of an endogenous reference compound (cholesterol) in the same sample, the difference between treated and untreated animals become statistically significant. 相似文献
59.
60.
In this work we investigate how a pattern imposed in a copolymer film at a certain distance from the surface propagates through the film onto an adsorbing heterogeneous surface. We bias the copolymer film to adopt a specified target pattern and then use simulation to design a surface pattern that helps the adsorbed film to maintain that target pattern. We examine the effect of varying the copolymer chain length, the size of the target pattern, and the distance from the surface where the target pattern is applied, z', on the extent of pattern transfer. For each chain length, target pattern, and z' we compare the energy of the system when a pattern is applied in the bulk to the energy when no pattern is applied in order to understand why a certain pattern size is transferred to the surface with higher fidelity than the others. At constant chain length, pattern transfer is best when the pattern size brings the energy of the system close to the energy when no pattern is applied. At constant pattern size, pattern transfer is best in the systems with longer chains. This is because longer chains are more likely to adsorb as brushes and loops which then helps transfer the pattern through the adsorbed film down to the surface. 相似文献