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161.
Rhodium- and copper-catalyzed methylenation reactions with trimethylsilyldiazomethane, triphenylphosphine, and 2-propanol were used to react chemoselectively with aldehydes, alkoxymethylketones, and trifluoromethylketones in substrates also containing a less reactive carbonyl group. Terminal alkenes were obtained in high yields, and no protecting group was necessary in the methylenation process. 相似文献
162.
Nemirowski A Reisenauer HP Romanski J Mloston G Schreiner PR 《The journal of physical chemistry. A》2008,112(50):13244-13248
The current case study focuses on the generation, identification, and characterization of two representative mono- and disubstituted alkyl phosphonatocarbenes by means of matrix isolation techniques in conjunction with density functional theory [B3LYP/6-311++G(d,p)] and coupled cluster [CCSD(T)/cc-pVXZ, X = D, T] computations. The EPR measurements identify both carbenes as triplet ground-state species with D values of 0.660 and 0.623 cm(-1), respectively, exhibiting persistency toward intramolecular reactions (the EPR signal observable in perfluoromethylcyclohexane up to around 70 K for the disubstituted molecule). While the reaction of the carbene center of the conformationally rich tetramethyl bisphosphonatocarbene with the CH bonds of the methyl groups leads to phosphaoxetane at room temperature, its fragmentation via a Wittig-type reaction during high vacuum flash pyrolysis (HVFP) results in dimethyl vinylphosphonate and methyl metaphosphate. The latter has been observed for the first time as an isolated entity. 相似文献
163.
Fractal Hamilton-Jacobi-KPZ equations 总被引:1,自引:0,他引:1
Grzegorz Karch Wojbor A. Woyczynski 《Transactions of the American Mathematical Society》2008,360(5):2423-2442
Nonlinear and nonlocal evolution equations of the form , where is a pseudodifferential operator representing the infinitesimal generator of a Lévy stochastic process, have been derived as models for growing interfaces in the case when the continuous Brownian diffusion surface transport is augmented by a random hopping mechanism. The goal of this paper is to study properties of solutions to this equation resulting from the interplay between the strengths of the ``diffusive' linear and ``hyperbolic' nonlinear terms, posed in the whole space , and supplemented with nonnegative, bounded, and sufficiently regular initial conditions.
164.
Silica mesoporous materials modified with manganese and iron were obtained by the hydrothermal method. Gold was introduced
to pure and modified silica materials by the direct hydrothermal and impregnation methods. Nitrogen adsorption/desorption
studies evidenced formation of the materials with large total surface area and mesoporous structure. Unmodified silica materials
showed regular pore arrangement. The uniform porous structure was distorted in the iron or manganese containing samples. XRD,
UV-Vis/DRS spectroscopy and temperature programmed reduction studies revealed changes of the nature of transition metal oxide
and gold species on the different preparation stages. The oxide species after drying were strongly dispersed and partially
incorporated to the silica framework. High temperature treatment led to the formation of extraframework Mn and Fe oxide species.
Complex processes of gold deposition were observed during hydrothermal synthesis and impregnation of modified silica materials.
The increase of the size of gold species was observed during calcination. The presence of transition metal oxides decreased
sintering of gold crystallites. 相似文献
165.
Although there are considerable data demonstrating that quantum mechanical hydrogen tunneling (HT) occurs in both enzymatic and nonenzymatic systems, little data exist that address the question of whether enzymes enhance the amount of HT relative to the corresponding nonenzymatic reactions. To investigate whether 3-oxo-Delta (5)-steroid isomerase (ketosteroid isomerase, KSI) enhances HT relative to the nonenzymatic (acetate-catalyzed) isomerization of Delta (5)-androstene-3,17-dione ( 1) to Delta (4)-androstene-3,17-dione ( 3), alpha-secondary deuterium kinetic isotope effects (KIE) at C-6 of the steroid were determined for both the KSI- and acetate-catalyzed isomerizations. The normal intrinsic secondary KIE for both wild type (WT) KSI (1.073 +/- 0.023) and acetate (1.031 +/- 0.010) suggest the possibility of coupled motion (CM)/HT in both the enzymatic and nonenzymatic systems. To assess the contribution of CM/HT in these reactions, the secondary KIE were also measured under conditions in which deuterium instead of hydrogen is transferred. The decrease in secondary KIE for WT (1.035 +/- 0.011) indicates the presence of CM/HT in the enzymatic reaction, whereas the acetate reaction shows no change in secondary KIE for deuterium transfer (1.030 +/- 0.009) and therefore no evidence for CM/HT. On the basis of these experiments, we propose that KSI enhances the CM/HT contribution to the rate acceleration over the solution reaction. Active site mutants of KSI (Y14F and D99A) yield secondary KIEs similar to that of WT, indicating that mutations at the hydrogen-bonding residues do not significantly decrease the contribution of CM/HT to the KSI reaction. 相似文献
166.
Sek S Xu S Chen M Szymanski G Lipkowski J 《Journal of the American Chemical Society》2008,130(17):5736-5743
Electrochemical scanning tunneling microscopy (EC-STM) has been applied to study the structure of the film formed by fusion of cholesterol suspensions and mixed dimyristoylphosphatidylcholine (DMPC)/cholesterol vesicles on a Au(111) electrode surface. It has been demonstrated that cholesterol molecules assemble at the gold support into several structures templated by the crystallography of the metal surface and involving flat or edge-on adsorbed molecules. Studies of the film formed by fusion of mixed DMPC/cholesterol vesicles revealed that ordered domains of either pure DMPC or pure cholesterol were formed. These results indicate that, at the metal surface, the molecules released by the rupture of a vesicle initially self-assemble into a well-ordered monolayer. The self-assembly is controlled by the hydrocarbon skeleton-metal surface interaction. In the case of mixed DMPC/cholesterol vesicles, the molecule-metal interactions induce segregation of the two components into single component domains. However, the molecule-metal interaction induced monolayer is a transient phenomenon. When more molecules accumulate at the surface, the molecule-molecule interactions dominate the assembly, and the monolayer is transformed into a bilayer. 相似文献
167.
Grzegorz Mlostoń Marta Woźnicka Józef Drabowicz Anthony Linden Heinz Heimgartner 《Helvetica chimica acta》2008,91(8):1419-1429
The reactions of 3‐phenyl‐1‐azabicyclo[1.1.0]butane with α‐chlorosulfenyl chlorides and sulfinyl chlorides lead to the corresponding sulfenamides and sulfinamides, respectively, which possess an azetidine ring. It is proposed that a two‐step mechanism occurs involving an intermediate carbenium ion, which is formed by the addition of the electrophile at the N‐atom and cleavage of the N(1)? C(3) bond. The structures of 9b and 10b are established by X‐ray crystallography. 相似文献
168.
Grzegorz K. Zieliński Prof. Dr. Karol Grela 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(28):9440-9454
Since olefin metathesis transformation has become a favored synthetic tool in organic synthesis, more and more distinct non‐metathetical reactions of alkylidene ruthenium complexes have been developed. Depending on the conditions applied, the same olefin metathesis catalysts can efficiently promote isomerization reactions, hydrogenation of C=C double bonds, oxidation reactions, and many others. Importantly, these transformations can be carried out in tandem with olefin metathesis reactions. Through addition of one portion of a catalyst, a tandem process provides structurally advanced products from relatively simple substrates without the need for isolation of the intermediates. These aspects not only make tandem catalysis very attractive from a practical point of view, but also open new avenues in (retro)synthetic planning. However, in the literature, the term “tandem process” is sometimes used improperly to describe other types of multi‐reaction sequences. In this Concept, a number of examples of tandem catalysis involving olefin metathesis are discussed with an emphasis on their synthetic value. 相似文献
169.
Grzegorz Mazur Marcin Makowski Roman Łazarski Radosław Włodarczyk Ewa Czajkowska Michał Glanowski 《International journal of quantum chemistry》2016,116(18):1370-1381
A unified, computer algebra system‐based scheme of code‐generation for computational quantum‐chemistry programs is presented. Generation of electron‐repulsion integrals and their derivatives as well as exchange‐correlation potential and its derivatives is discussed. Application to general‐purpose computing on graphics processing units is considered. 相似文献
170.