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51.
Gemma M. Locke Dr. Stefan S. R. Bernhard Prof. Dr. Mathias O. Senge 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(18):4590-4647
Nonconjugated hydrocarbons, like bicyclo[1.1.1]pentane, bicyclo[2.2.2]octane, triptycene, and cubane are a unique class of rigid linkers. Due to their similarity in size and shape they are useful mimics of classic benzene moieties in drugs, so-called bioisosteres. Moreover, they also fulfill an important role in material sciences as linear linkers, in order to arrange various functionalities in a defined spatial manner. In this Review article, recent developments and usages of these special, rectilinear systems are discussed. Furthermore, we focus on covalently linked, nonconjugated linear arrangements and discuss the physical and chemical properties and differences of individual linkers, as well as their application in material and medicinal sciences. 相似文献
52.
Bernhard Wölfl Dr. Guillaume Mata Prof. Alois Fürstner 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(1):255-259
The macrocyclic core of the cytotoxic marine natural product callyspongiolide ( 1 ) was forged by ring-closing alkyne metathesis (RCAM) of an ynoate precursor using a molybdenum alkylidyne complex endowed with triarylsilanolate ligands as the catalyst. This result is remarkable in view of the failed attempts documented in the literature at converting electron deficient alkynes with the aid of more classical catalysts. The subsequent Z-selective semi-reduction of the resulting cycloalkyne by hydrogenation over nickel boride required careful optimization in order to minimize overreduction and competing dehalogenation of the compound's alkenyl iodide terminus as needed for final attachment of the side chain of 1 by Sonogashira coupling. The required cyclization precursor itself was prepared via Kocienski olefination. 相似文献
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Bernhard G. Bodmann Martin Ehler Manuel Gräf 《Journal of Theoretical Probability》2018,31(4):2167-2193
We aim to compute the first few moments of a high-dimensional random vector from the first few moments of a number of its low-dimensional projections. To this end, we identify algebraic conditions on the set of low-dimensional projectors that yield explicit reconstruction formulas. We also provide a computational framework, with which suitable projectors can be derived by solving an optimization problem. Finally, we show that randomized projections permit approximate recovery. 相似文献
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Gated Channels and Selectivity Tuning of CO2 over N2 Sorption by Post‐Synthetic Modification of a UiO‐66‐Type Metal–Organic Framework 下载免费PDF全文
Alexander Kronast Sebastian Eckstein Dr. Peter T. Altenbuchner Dr. Konrad Hindelang Dr. Sergei I. Vagin Prof. Dr. Bernhard Rieger 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(36):12800-12807
The highly porous and stable metal–organic framework (MOF) UiO‐66 was altered using post‐synthetic modifications (PSMs). Prefunctionalization allowed the introduction of carbon double bonds into the framework through a four‐step synthesis from 2‐bromo‐1,4‐benzenedicarboxylic acid; the organic linker 2‐allyl‐1,4‐benzenedicarboxylic acid was obtained. The corresponding functionalized MOF (UiO‐66‐allyl) served as a platform for further PSMs. From UiO‐66‐allyl, epoxy, dibromide, thioether, diamine, and amino alcohol functionalities were synthesized. The abilities of these compounds to adsorb CO2 and N2 were compared, which revealed the structure–selectivity correlations. All synthesized MOFs showed profound thermal stability together with an increased ability for selective CO2 uptake and molecular gate functionalities at low temperatures. 相似文献
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Miaoyong Cao John Wesson Kyriakos Loufakis Bernhard Wunderlich Martin Möller 《Molecular Crystals and Liquid Crystals》2013,570(2-4):231-241
Three cyclic methyl and ethyl substituted silanes were synthesized and their thermal properties analyzed. All show a plastic crystalline state which permits also ring and/or side-chain conformational motion as judged from the enthalpies of transition to the isotropic state. Heat capacity data and entropies of disordering into the plastic crystal leave open the possibility of a condis (conformationally disordered) state below the plastic crystal state with a continuous, transitionless freezing of the conformational motion at lower temperature. 相似文献
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