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991.
R. G. Gasanov S. O. Videnskaya V. V. Pinjaskin I. V. Stankevich 《Russian Chemical Bulletin》1995,44(3):437-439
The AM1 method was used to analyze the factors that correlate with regioselectivity in the addition of radicals to 1,2-disubstituted unsaturated compounds. The rate constants of the addition of.CCl3 radicals to RCH=CHC(O)X (R = Ph, Me; X = N-pyrrolidyl) were determined by ESR. The analysis of the spin density distribution in mono- and 1,2-disubstituted alkenes and the experimental values for the rate constants of the addition of.CCl3 radicals to these alkenes allowed the authors to conclude that the efficiency of the addition of.CC13 to unsaturated compounds depends only on steric effects.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 452–455, March, 1995. 相似文献
992.
Features of the ignition kinetics of an H2/air mixture in the supersonic flow behind an inclined shock front are analyzed when asymmetric vibrations of a small amount (<1%) of O3 molecules specially introduced into the initial mixture are excited by 9.7 μm wavelength radiation. It is shown that this radiation leads to intensification of the chain reactions and makes it possible to organize combustion at small distances from the front (of the order of 1 m) of even relatively weak shocks at small values of the laser radiation energies absorbed by the gas. This method of initiating combustion in a supersonic flow is 10–100 times more efficient than the thermal method.__________Translated from Izvestiya Rossiiskoi Academii Nauk, Mekhanika Zhidkosti i Gaza, No. 2, 2005, pp. 157–167.Original Russian Text Copyright © 2005 by Lukhovitskii, Starik, and Titova. 相似文献
993.
Inside Back Cover: Intermolecular Enantioselective Dearomatization Reaction of β‐Naphthol Using meso‐Aziridine: A Bifunctional In Situ Generated Magnesium Catalyst (Angew. Chem. Int. Ed. 7/2015)
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994.
On the Role of the Electronic Structure of the Heteronuclear Oxide Cluster [Ga2Mg2O5].+ in the Thermal Activation of Methane and Ethane: An Unusual Doping Effect
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Dr. Jilai Li Dr. Xiao‐Nan Wu Dr. Maria Schlangen Dr. Shaodong Zhou Dr. Patricio González‐Navarrete Dr. Shiya Tang Prof. Dr. Helmut Schwarz 《Angewandte Chemie (International ed. in English)》2015,54(17):5074-5078
The reactivity of the heteronuclear oxide cluster [Ga2Mg2O5].+, bearing an unpaired electron at a bridging oxygen atom (Ob.?), towards methane and ethane has been studied using Fourier transform ion cyclotron resonance mass spectrometry (FT‐ICR‐MS). Hydrogen‐atom transfer (HAT) from both methane and ethane to the cluster ion is identified experimentally. The reaction mechanisms of these reactions are elucidated by state‐of‐the‐art quantum chemical calculations. The roles of spin density and charge distributions in HAT processes, as revealed by theory, not only deepen our mechanistic understanding of C? H bond activation but also provide important guidance for the rational design of catalysts by pointing to the particular role of doping effects. 相似文献
995.
Graphene Liquid Marbles as Photothermal Miniature Reactors for Reaction Kinetics Modulation
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Wei Gao Hiang Kwee Lee Dr. Jonathan Hobley Prof. Tianxi Liu Dr. In Yee Phang Prof. Xing Yi Ling 《Angewandte Chemie (International ed. in English)》2015,54(13):3993-3996
We demonstrate the fabrication of graphene liquid marbles as photothermal miniature reactors with precise temperature control for reaction kinetics modulation. Graphene liquid marbles show rapid and highly reproducible photothermal behavior while maintaining their excellent mechanical robustness. By tuning the applied laser power, swift regulation of graphene liquid marble’s surface temperature between 21–135 °C and its encapsulated water temperature between 21–74 °C are demonstrated. The temperature regulation modulates the reaction kinetics in our graphene liquid marble, achieving a 12‐fold superior reaction rate constant for methylene blue degradation than at room temperature. 相似文献
996.
Highly Stereoselective Synthesis of Natural‐Product‐Like Hybrids by an Organocatalytic/Multicomponent Reaction Sequence
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M. Sc. Radell Echemendía M. Sc. Alexander F. de La Torre M. Sc. Julia L. Monteiro M. Sc. Michel Pila Prof. Dr. Arlene G. Corrêa Prof. Dr. Bernhard Westermann Prof. Dr. Daniel G. Rivera Prof. Dr. Márcio W. Paixão 《Angewandte Chemie (International ed. in English)》2015,54(26):7621-7625
In an endeavor to provide an efficient route to natural product hybrids, described herein is an efficient, highly stereoselective, one‐pot process comprising an organocatalytic conjugate addition of 1,3‐dicarbonyls to α,β‐unsaturated aldehydes followed by an intramolecular isocyanide‐based multicomponent reaction. This approach enables the rapid assembly of complex natural product hybrids including up to four different molecular fragments, such as hydroquinolinone, chromene, piperidine, peptide, lipid, and glycoside moieties. The strategy combines the stereocontrol of organocatalysis with the diversity‐generating character of multicomponent reactions, thus leading to structurally unique peptidomimetics integrating heterocyclic, lipidic, and sugar moieties. 相似文献
997.
Cocrystal Formation through Mechanochemistry: from Neat and Liquid‐Assisted Grinding to Polymer‐Assisted Grinding
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Dr. Dritan Hasa Gabriela Schneider Rauber Prof. Dario Voinovich Prof. William Jones 《Angewandte Chemie (International ed. in English)》2015,54(25):7371-7375
Mechanochemistry is an effective method for the preparation of multicomponent crystal systems. In the present work, we propose an alternative to the established liquid‐assisted grinding (LAG) approach. Polymer‐assisted grinding (POLAG) is demonstrated to provide a new class of catalysts for improving reaction rate and increasing product diversity during mechanochemical cocrystallization reactions. We demonstrate that POLAG provides advantages comparable to the conventional liquid‐assisted process, whilst eliminating the risk of unwanted solvate formation as well as enabling control of resulting particle size. It represents a new approach for the development of functional materials through mechanochemistry, and possibly opens new routes toward the understanding of the mechanisms and pathways of mechanochemical cocrystal formation. 相似文献
998.
Direct Detection of the Superoxide Anion as a Stable Intermediate in the Electroreduction of Oxygen in a Non‐Aqueous Electrolyte Containing Phenol as a Proton Source
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Prof. Zhangquan Peng Dr. Yuhui Chen Prof. Peter G. Bruce Prof. Ye Xu 《Angewandte Chemie (International ed. in English)》2015,54(28):8165-8168
The non‐aqueous Li–air (O2) battery has attracted intensive interest because it can potentially store far more energy than today′s batteries. Presently Li–O2 batteries suffer from parasitic reactions owing to impurities, found in almost all non‐aqueous electrolytes. Impurities include residual protons and protic compounds that can react with oxygen species, such as the superoxide (O2?), a reactive, one‐electron reduction product of oxygen. To avoid the parasitic reactions, it is crucial to have a fundamental understanding of the conditions under which reactive oxygen species are generated in non‐aqueous electrolytes. Herein we report an in situ spectroscopic study of oxygen reduction on gold in a dimethyl sulfoxide electrolyte containing phenol as a proton source. It is shown directly that O2?, not HO2, is the first stable intermediate during the oxygen reduction process to hydrogen peroxide. The unusual stability of O2? is explained using density functional theory (DFT) calculations. 相似文献
999.
Substrate‐Tuned Catalysis of the Radical S‐Adenosyl‐L‐Methionine Enzyme NosL Involved in Nosiheptide Biosynthesis
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Xinjian Ji Dr. Yongzhen Li Prof. Dr. Wei Ding Prof. Dr. Qi Zhang 《Angewandte Chemie (International ed. in English)》2015,54(31):9021-9024
NosL is a radical S‐adenosyl‐L ‐methionine (SAM) enzyme that converts L ‐Trp to 3‐methyl‐2‐indolic acid, a key intermediate in the biosynthesis of a thiopeptide antibiotic nosiheptide. In this work we investigated NosL catalysis by using a series of Trp analogues as the molecular probes. Using a benzofuran substrate 2‐amino‐3‐(benzofuran‐3‐yl)propanoic acid (ABPA), we clearly demonstrated that the 5′‐deoxyadenosyl (dAdo) radical‐mediated hydrogen abstraction in NosL catalysis is not from the indole nitrogen but likely from the amino group of L ‐Trp. Unexpectedly, the major product of ABPA is a decarboxylated compound, indicating that NosL was transformed to a novel decarboxylase by an unnatural substrate. Furthermore, we showed that, for the first time to our knowledge, the dAdo radical‐mediated hydrogen abstraction can occur from an alcohol hydroxy group. Our study demonstrates the intriguing promiscuity of NosL catalysis and highlights the potential of engineering radical SAM enzymes for novel activities. 相似文献
1000.
Metal‐Catalyzed β‐Functionalization of Michael Acceptors through Reductive Radical Addition Reactions
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Dr. Jan Streuff Prof. Dr. Andreas Gansäuer 《Angewandte Chemie (International ed. in English)》2015,54(48):14232-14242
Transition‐metal‐catalyzed radical reactions are becoming increasingly important in modern organic chemistry. They offer fascinating and unconventional ways for connecting molecular fragments that are often complementary to traditional methods. In particular, reductive radical additions to α,β‐unsaturated compounds have recently gained substantial attention as a result of their broad applicability in organic synthesis. This Minireview critically discusses the recent landmark achievements in this field in context with earlier reports that laid the foundation for today′s developments. 相似文献