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951.
Aerobic Double Dehydrogenative Cross Coupling between Cyclic Saturated Ketones and Simple Arenes 下载免费PDF全文
Dr. Nicolas Gigant Prof. Dr. Jan‐E. Bäckvall 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(20):5890-5894
The synthesis of 3‐aryl‐2‐cyclohexenones is a topic of current interest as they are not only privileged structures in bioactive molecules, but they are also relevant feedstocks for the synthesis of substituted phenols or anilines, which are ubiquitous structural elements both in drug design and medicinal chemistry. A simple and sustainable one‐pot aerobic double dehydrogenative reaction under mild conditions for the introduction of arenes in the β‐position of cyclic ketones has been developed. Starting from the corresponding saturated ketone, this reaction sequence proceeds under relatively low Pd catalyst loading and involves catalytic amounts of electron‐transfer mediators (ETMs) under ambient oxygen pressure. 相似文献
952.
Multicomponent,Flow Diazotization/Mizoroki–Heck Coupling Protocol: Dispelling Myths about Working with Diazonium Salts 下载免费PDF全文
Dr. Kumara S. Nalivela Michael Tilley Dr. Michael A. McGuire Prof. Michael G. Organ 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(22):6603-6607
A single pass flow diazotization/Mizoroki–Heck protocol has been developed for the production of cinnimoyl and styryl products. The factors that govern aryl diazonium salt stability have been examined in detail leading to the development of a MeOH/DMF co‐solvent system in which the diazonium salts can be generated in the presence of all other reaction components and then coupled selectively to give the desired products. Finally the key role of the reaction quench for flow reactions has been demonstrated. 相似文献
953.
Exploring the Molecular Structure of Imidazolium–Silica‐Based Nanoparticle Networks by Combining Solid‐State NMR Spectroscopy and First‐Principles Calculations 下载免费PDF全文
Dr. Marie‐Alexandra Neouze Martin Kronstein Dr. Marco Litschauer Dr. Michael Puchberger Dr. Cristina Coelho Prof. Christian Bonhomme Prof. Christel Gervais Dr. Frederik Tielens 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(46):15188-15196
A DFT‐based molecular model for imidazolium–silica‐based nanoparticle networks (INNs) is presented. The INNs were synthesized and characterized by using small‐angle X‐ray scattering (SAXS), NMR spectroscopy, and theoretical ab initio calculations. 11B and 31P HETCOR CP MAS experiments were recorded. Calculated 19F NMR spectroscopy results, combined with the calculated anion–imidazolium (IM) distances, predicted the IM chain density in the INN, which was also confirmed from thermogravimetric analysis/mass spectrometry results. The presence of water molecules trapped between the nanoparticles is also suggested. First considerations on possible π–π stacking between the IM rings are presented. The predicted electronic properties confirm the photoluminescence emissions in the correct spectral domain. 相似文献
954.
Mechanistic Insights into RNA Transphosphorylation from Kinetic Isotope Effects and Linear Free Energy Relationships of Model Reactions 下载免费PDF全文
Haoyuan Chen Dr. Timothy J. Giese Dr. Ming Huang Prof. Dr. Kin‐Yiu Wong Prof. Dr. Michael E. Harris Prof. Dr. Darrin M. York 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(44):14336-14343
Phosphoryl transfer reactions are ubiquitous in biology and the understanding of the mechanisms whereby these reactions are catalyzed by protein and RNA enzymes is central to reveal design principles for new therapeutics. Two of the most powerful experimental probes of chemical mechanism involve the analysis of linear free energy relations (LFERs) and the measurement of kinetic isotope effects (KIEs). These experimental data report directly on differences in bonding between the ground state and the rate‐controlling transition state, which is the most critical point along the reaction free energy pathway. However, interpretation of LFER and KIE data in terms of transition‐state structure and bonding optimally requires the use of theoretical models. In this work, we apply density‐functional calculations to determine KIEs for a series of phosphoryl transfer reactions of direct relevance to the 2′‐O‐transphosphorylation that leads to cleavage of the phosphodiester backbone of RNA. We first examine a well‐studied series of phosphate and phosphorothioate mono‐, di‐ and triesters that are useful as mechanistic probes and for which KIEs have been measured. Close agreement is demonstrated between the calculated and measured KIEs, establishing the reliability of our quantum model calculations. Next, we examine a series of RNA transesterification model reactions with a wide range of leaving groups in order to provide a direct connection between observed Brønsted coefficients and KIEs with the structure and bonding in the transition state. These relations can be used for prediction or to aid in the interpretation of experimental data for similar non‐enzymatic and enzymatic reactions. Finally, we apply these relations to RNA phosphoryl transfer catalyzed by ribonuclease A, and demonstrate the reaction coordinate–KIE correlation is reasonably preserved. A prediction of the secondary deuterium KIE in this reaction is also provided. These results demonstrate the utility of building up knowledge of mechanism through the systematic study of model systems to provide insight into more complex biological systems such as phosphoryl transfer enzymes and ribozymes. 相似文献
955.
Synthesis of Single‐Crystalline Spinel LiMn2O4 Nanorods for Lithium‐Ion Batteries with High Rate Capability and Long Cycle Life 下载免费PDF全文
Xiuqiang Xie Dr. Dawei Su Dr. Bing Sun Jinqiang Zhang Prof. Dr. Chengyin Wang Prof. Dr. Guoxiu Wang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(51):17125-17131
The long‐standing challenge associated with capacity fading of spinel LiMn2O4 cathode material for lithium‐ion batteries is investigated. Single‐crystalline spinel LiMn2O4 nanorods were successfully synthesized by a template‐engaged method. Porous Mn3O4 nanorods were used as self‐sacrificial templates, into which LiOH was infiltrated by a vacuum‐assisted impregnation route. When used as cathode materials for lithium‐ion batteries, the spinel LiMn2O4 nanorods exhibited superior long cycle life owing to the one‐dimensional nanorod structure, single‐crystallinity, and Li‐rich effect. LiMn2O4 nanorods retained 95.6 % of the initial capacity after 1000 cycles at 3C rate. In particular, the nanorod morphology of the spinel LiMn2O4 was well‐preserved after a long‐term cycling, suggesting the ultrahigh structural stability of the single crystalline spinel LiMn2O4 nanorods. This result shows the promising applications of single‐crystalline spinel LiMn2O4 nanorods as cathode materials for lithium‐ion batteries with high rate capability and long cycle life. 相似文献
956.
CuII/TEMPO‐Promoted One‐Pot Synthesis of Highly Substituted Pyrimidines from Amino Acid Esters 下载免费PDF全文
Dr. Nini Zhou Tao Xie Zhongle Li Prof. Dr. Zhixiang Xie 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(52):17311-17314
A novel, Cu(OAc)2/TEMPO promoted one‐step approach for the preparation of fully substituted pyrimidines from readily available amino acid esters has been described. In this reaction, the amino acid esters act as the only N?C sources for the construction of corresponding pyrimidines. The mechanism of this process includes oxidative dehydrogenation, the generation of an imine radical, and a formal [3+3] cycloaddition. This methodology proves to be a high atom‐economic and straightforward strategy for the synthesis of pyrimidines and diverse substrates which are substituted by various functional groups have been afforded in moderate to good yield. 相似文献
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