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271.
Anu Naik Liu Meina Manfred Zabel Dr. Oliver Reiser Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(5):1624-1628
The palladium‐catalyzed aerobic oxidation of alkenes and especially styrenes (Wacker oxidation) by using chiral pseudo C2‐symmetrical bis(isonitrile) ligands in the absence of further cocatalysts gives rise to methyl ketones in a highly chemoselective manner. The palladium bis(isonitrile) catalyst was characterized by NMR spectroscopy and X‐ray structure analysis, revealing a dissymmetric coordination of palladium by the two isonitrile moieties. 相似文献
272.
Diffusion in fluids is analyzed at non-classical conditions, intermediate between the Knudsen and Fickian limits. The fluid is considered in the framework of the Einstein’s diffusion evolution equation involving expansions of the density distribution in powers of displacement and time. The standard truncation of these expansions results in the classical model of diffusion; however, higher-order terms lead to a departure from classical behavior. This has not been studied or discussed adequately in the literature previously.Here, we present an exact solution of the Einstein’s diffusion evolution equation without truncation of the density expansions. This solution illustrates limitations in the classical truncations and demonstrates non-classical effects due to large mean free paths, λ. In particular, this new solution shows that, at large λ, there are significant quantitative deviations from classical diffusion profiles. In addition, this solution demonstrates a dramatic change in the diffusion mechanism from the state where the molecular motions are predominantly ballistic to one of molecular chaos. This has implications for fundamentals of fluids between the Knudsen and Fickian limits, and for a variety of fields where evolution of a system includes random, multi-scale displacement of particles, such as nanotechnology, vacuum techniques, turbulence, and astrophysics. 相似文献
273.
Christine A. Bange Prof. Dr. Rory Waterman 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(36):12598-12605
Despite significant advances, metal‐catalyzed hydrophosphination has ample room for discovery, growth, and development. Many of the key successes in metal‐catalyzed hydrophosphination over the last decade have indicated what is needed and what is yet to come. Reactivity that is absent from the literature also speaks to the challenges in catalytic hydrophosphination. This Concept article discusses and highlights recent developments that address the ongoing challenges, and identifies areas in metal‐catalyzed hydrophosphination that are underdeveloped. Advances in product selectivity, catalyst design, and both unsaturated and phosphine substrates illustrate the ongoing development of the field. Like all catalytic transformations, the benefits are realized through catalyst, ligand, and conditions, and consideration of those features are the route to a yet more efficient and broadly applicable reaction. 相似文献
274.
Hantzsch Ester as a Photosensitizer for the Visible‐Light‐Induced Debromination of Vicinal Dibromo Compounds
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Wenxin Chen Huachen Tao Wenhao Huang Guoqiang Wang Prof. Dr. Shuhua Li Prof. Dr. Xu Cheng Prof. Dr. Guigen Li 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(28):9546-9550
The debromination of vicinal dibromo compounds to generate alkenes usually requires harsh reaction conditions and the addition of catalysts. Just recently the visible‐light‐induced debromination of vicinal dibromo compounds emerged as a possible alternative to commonly used methods, but the substrate scope of this reaction is limited and a photocatalyst is necessary for the successful conversion of the starting compounds. A catalyst‐free visible‐light‐induced debromination of vicinal dibromo compounds with a base‐activated Hantzsch ester as photosensitizer is reported. The method has a wide substrate scope and a broad functional‐group compatibility. 相似文献
275.
Jordanka Petrova Nikolai G. Vassilev Marko Kirilov 《Phosphorus, sulfur, and silicon and the related elements》2013,188(3-4):457-463
Abstract The reaction of the lithium derivative of diethyl ester of phenylmethanephosphonic acid (1-Li) with alkanones, cycloalkanones, alkylaryl and diarylketones 2s-b is studied at -70°C in THF. The corresponding adducts-diethyl esters of l-phenyl-2,2-dialkyl(phenyl)-2-hydroxyethanephosphonic acids 3s-h are isolated, their yields being usually higher at short reaction time. The olefination of 3-Li as well as of 3 (both by thermolysis or in acidic media) proceeds in low degree, while in the case of 3-Na the yields of alkenes 4 are good. The relative configurations of 3b. 31 and 3g are determined by IR and NMR-spectra, as well as by their stereospecific olefination. “Threo”-stereoselectivity of the addition stage of the reaction of 1-Li with 2b, 21 and 2g is observed, the “threo”/“erythro” ratio remaining independent on the reaction time. 相似文献
276.
In the crystallographic literature, there is an ever-increasing number of publications on crystals that are referred to as ‘new non-linear optical materials’, many of them reporting salts of amino acids. However, the term NLO material is used improperly in most cases. In fact, the establishment of any crystal species as such a material requires several experimental and computational procedures, which are seldom satisfied when characterizing a supposedly new species. Here, some frequent hazards and problems are addressed and observations of papers reporting amino acid compounds as supposedly new NLO materials are made. 相似文献
277.
278.
Fluid dynamic properties of blood flow are implicated in cardiovascular diseases. The interaction between the blood flow and the wall occurs through the direct transmission of forces, and through the dominating influence of the flow on convective transport processes. Controlled, in vitro testing in simple geometric configurations has provided much data on the cellular-level responses of the vascular walls to flow, but a complete, mechanistic explanation of the pathogenic process is lacking. In the interim, mapping the association between local haemodynamics and the vascular response is important to improve understanding of the disease process and may be of use for prognosis. Moreover, establishing the haemodynamic environment in the regions of disease provides data on flow conditions to guide investigations of cellular-level responses. 相似文献
279.
Daniel J. Tao Dr. Mikko Muuronen Yuriy Slutskyy Alexander Le Prof. Filipp Furche Prof. Larry E. Overman 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(26):8786-8790
The stereochemical outcome of reactions of chiral nucleophilic trisubstituted acetonide radicals with electron‐deficient alkenes is dictated by a delicate balance between destabilizing non‐bonding interactions and stabilizing hydrogen‐bonding between substituents on the α and β carbons. 相似文献
280.