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Dennis Jansen Johannes Gramüller Felix Niemeyer Torsten Schaller Matthias C. Letzel Stefan Grimme Hui Zhu Ruth M. Gschwind Jochen Niemeyer 《Chemical science》2020,11(17):4381
Organocatalysis has revolutionized asymmetric synthesis. However, the supramolecular interactions of organocatalysts in solution are often neglected, although the formation of catalyst aggregates can have a strong impact on the catalytic reaction. For phosphoric acid based organocatalysts, we have now established that catalyst–catalyst interactions can be suppressed by using macrocyclic catalysts, which react predominantly in a monomeric fashion, while they can be favored by integration into a bifunctional catenane, which reacts mainly as phosphoric acid dimers. For acyclic phosphoric acids, we found a strongly concentration dependent behavior, involving both monomeric and dimeric catalytic pathways. Based on a detailed experimental analysis, DFT-calculations and direct NMR-based observation of the catalyst aggregates, we could demonstrate that intermolecular acid–acid interactions have a drastic influence on the reaction rate and stereoselectivity of asymmetric transfer-hydrogenation catalyzed by chiral phosphoric acids.Supramolecular acid–acid interactions lead to competing monomeric and dimeric pathways in phosphoric acid catalysis – so that stereoselectivities depend on catalyst concentration. 相似文献
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Huatian Shi Jianhui Xie William W. Y. Lam Wai-Lun Man Chi-Keung Mak Shek-Man Yiu Hung Kay Lee Tai-Chu Lau 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(56):12895-12899
The synthesis and X-ray structure of a new manganese(V) mesitylimido complex with a tetraamido macrocyclic ligand (TAML), [MnV(TAML)(N-Mes)]− ( 1 ), are reported. Compound 1 is oxidized by [(p-BrC6H4)3N ]+.[SbCl6]− and the resulting MnVI species readily undergoes H-atom transfer and nitrene transfer reactions. 相似文献
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Abdusalom A. Suleymanov Martin Doll Dr. Albert Ruggi Dr. Rosario Scopelliti Dr. Farzaneh Fadaei-Tirani Prof. Kay Severin 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(25):10043-10047
Tetraarylethenes are obtained by acid-induced coupling of vinyl triazenes with aromatic compounds. This new C−H activation route for the synthesis of aggregation-induced emission luminogens is simple, fast, and versatile. It allows the direct grafting of triarylethenyl groups onto a variety of aromatic compounds, including heterocycles, supramolecular hosts, biologically relevant molecules, and commercial polymers. 相似文献
6.
Kay E. B. Doncom Helen Willcock Rachel K. O'Reilly 《Journal of polymer science. Part A, Polymer chemistry》2014,52(21):3026-3031
A diblock copolymer consisting of tetrahydropyranyl acrylate (THPA) as a pH‐deprotectable block, and a permanently hydrophobic block, methyl acrylate, was synthesized by RAFT polymerization using a quaternary amine functionalized, hydrophilic, RAFT chain transfer agent. The polymer self‐assembled in water to form vesicles with Dh = 130 nm, as determined by DLS and cryogenic transmission electron microscopy. Acid catalyzed deprotection of the THPA units to yield acrylic acid resulted in a vesicle to micelle morphology transition, as evidenced by the decrease in hydrodynamic diameter to Dh = 19 nm and the observation of micelles by dry state transmission electron microscopy. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 3026–3031 相似文献
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This paper proposes a method to improve the reliability of construction schedules by optimizing schedule robustness of construction projects. The schedule robustness is measured by a criterion evaluating the impact of deviations from the initial schedule on the makespan, which arise during the realization phase of a construction project. (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
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A cyber-physical system (CPS) is a coupled system integrating computing, networking, and physical processes. Through actuation, cyber-physical systems control the physical processes, usually with feedback loops, where the physical processes affect computing and networking processes, and vice versa. In civil engineering, the most common fields of CPS applications are structural health monitoring (SHM) and structural control. A typical CPS task is the assessment of a structure based on (i) collected measurement data and (ii) a corresponding model. However, for an accurate and precise assessment of a structure, the CPS itself must be modeled and evaluated. In this paper, a conceptual modeling and evaluation approach is proposed, in which each part of a CPS is evaluated individually. In this study, the conceptual approach is presented for modeling and evaluation of CPS in civil engineering. The evaluation is based on an abstract approach allowing a discussion of a principle (i.e. general) model structure of a CPS, identifying critical issues to be studied in more detail in future research. (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
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Sylvain Sudan Damien W. Chen Cesare Berton Farzaneh Fadaei-Tirani Kay Severin 《Angewandte Chemie (International ed. in English)》2023,62(9):e202218072
A water-soluble coordination cage was obtained by reaction of Pd(NO3)2 with a 1,3-di(pyridin-3-yl)benzene ligand featuring a short PEG chain. The cavity of the metal-organic cage contains one nitrate anion, which is readily replaced by chloride. The apparent association constant for chloride binding in buffered aqueous solution is Ka=1.8(±0.1)×105 M−1. This value is significantly higher than what has been reported for other macrocyclic chloride receptors. The heavier halides Br− and I− compete with binding or self-assembly, but the receptor displays very good selectivity over common anions such as phosphate, acetate, carbonate, and sulfate. A further increase of the chloride binding affinity by a factor of 3 was achieved using a fluorinated dipyridyl ligand. 相似文献