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71.
Tetracyanoquinodimethane Reduction by Complexed Guanidinyl‐Functionalized Aromatic Compounds
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Hendrik Herrmann Alexandra Ziesak Ute Wild Simone Leingang David Schrempp Norbert Wagner Prof. Dr. Johannes Beck Dr. Elisabeth Kaifer Prof. Dr. Hubert Wadepohl Prof. Dr. Hans‐Jörg Himmel 《Chemphyschem》2014,15(2):351-365
In this work, we report on the reduction of tetracyanoquinodimethane (TCNQ) with dicationic complexes of guanidinyl‐functionalized aromatic (GFA) electron donors. In contrast to reduction with free GFAs, milder reduction conditions were achieved, and this led to semiconducting materials with extended TCNQ π stacking. The charge on the TCNQ units was estimated from the structural data obtained by single‐crystal X‐ray diffraction analysis and from IR spectroscopic data. The electrical conductivity was studied and the activation energy of the semiconducting materials was estimated from the temperature dependence of the conductivity. 相似文献
72.
Hendrik Gruß Prof. Dr. Norbert Sewald 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(24):5328-5340
Pd-mediated reactions have emerged as a powerful tool for the site-selective and bioorthogonal late-stage diversification of amino acids, peptides and related compounds. Indole moieties of tryptophan derivatives are susceptible to C2H-activation, whereas halogenated aromatic amino acids such as halophenylalanines or halotryptophans provide a broad spectrum of different functionalisations. The compatibility of transition-metal-catalysed cross-couplings with functional groups in peptides, other biologically active compounds and even proteins has been demonstrated. This Review primarily compiles the application of different cross-coupling reactions to modify halotryptophans, halotryptophan containing peptides or halogenated, biologically active compounds derived from tryptophan. Modern approaches use regio- and stereoselective biocatalytic strategies to generate halotryptophans and derivatives on a preparative scale. The combination of bio- and chemocatalysis in cascade reactions is given by the biocompatibility and bioorthogonality of Pd-mediated reactions. 相似文献
73.
Moritz Balkenhohl Harish Jangra Ilya S. Makarov Shu‐Mei Yang Hendrik Zipse Paul Knochel 《Angewandte Chemie (International ed. in English)》2020,59(35):14992-14999
The development of a predictive model towards site‐selective deprotometalation reactions using TMPZnCl?LiCl is reported (TMP=2,2,6,6‐tetramethylpiperidinyl). The pKa values of functionalized N‐, S‐, and O‐heterocycles, arenes, alkenes, or alkanes were calculated and compared to the experimental deprotonation sites. Large overlap (>80 %) between the calculated and empirical deprotonation sites was observed, showing that thermodynamic factors strongly govern the metalation regioselectivity. In the case of olefins, calculated frozen state energies of the deprotonated substrates allowed a more accurate prediction. Additionally, various new N‐heterocycles were analyzed and the metalation regioselectivities rationalized using the predictive model. 相似文献
74.
Rhodium PCcarbeneP complexes 1‐L {L=PPh3, PPh2(C6F5)} react with isothiocyanate, carbodiimide and disulphide to enable C?S, C?N and S?S bond cleavage. The cleaved molecules are sequestered by the metal center and the pincer alkylidene linkage, forming η2‐coordinated sulfide or imide centered pincer complexes. When a C?S or S?S bond is cleaved, the resulting complexes can bridge two rhodium centers through sulphur forming dimeric complexes and eliminating a monodentate phosphine ligand. 相似文献
75.
Im Rahmen des Graduiertenkollegs “Hochreaktive Mehrfachbindungssysteme” hatten G. Erker und J. Grobe vom 16. bis 18. November 1994 schon zum zweiten Mal nach Münster eingeladen. “Organic and Inorganic Chemistry of Reactive C=X π-Systems” waren diesmal das Thema. 相似文献
76.
Reaction between O,O-diethyl-S-phenyl phosphorothiolate and lithium dialkylamides results in the displacement of the PhS substituent by the R2N group. With Grignard reagents, the same substrate gives products of the nucleophilic substitution at both the phosphorus and the sulfur atom. 相似文献
77.
78.
Hendrik F. Hameka Silvio L. Emery George R. Famini James O. Jensen Joseph M. Leonard Dennis J. Reutter 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1-4):373-388
Abstract We report the computed equilibrium geometries and vibrational infrared frequencies of a group of thirteen mercaptans and sulfides. The computations were based on the Gaussian 86 Program Package utilizing 3-21G basis sets. The theoretical bond distances and bond angles are in agreement with the available experimental data. The agreement between computed frequencies and available experimental values seems reasonable. We also used the computations as guidelines for the assignment of available experimental infrared frequencies. We believe that it is possible to make reliable frequency predictions by combining computations with available experimental data for groups of similar molecules. However, it is necessary to introduce different correction factors for different types of vibrational modes if we use 3-21G basis sets. 相似文献
79.
Eberhard Neumann Elvira Boldt Barbara Rauer Hendrik Wolf Hai Won Chang 《Macromolecular Symposia》1988,17(1):1-16
The nicotinic acetylcholine receptor (nAcChR) of the electric organ of Torpedo californica fish exhibits a pronounced hysteresis loop in the high affinity binding of the neurotransmitter acetylcholine (AcCh). When increasing amounts of AcCh are added (pulse mode) an extremely long-lived, metastable conformer distribution is obtained (lower hysteresis branch) between low affinity AcCh binding states (Rl) and high (Rh) and very high (Rvh) affinity states. Dialysis conditions always lead to the equilibrium binding curve (upper hysteresis branch; K̄A = 5 × 10−9M, 4°C; one A bound to the R-monomer of Mr ≈ 290 000). Cyclic, pulse mode addition and dilution of AcCh results in scanning loops within the main hysteresis. The kinetic analysis of the changes in free and bound AcCh during the open-system conditions of dialysis, that releases the metastability, shows that the AcCh (A) binding proceeds along an induced-fit pathway according to A+Rh ⇋ ARn ⇋ ARvh. The rate constant of the step ARh → ARvh is k2 = 6 × 10−3s−1 and that of the reverse step is k−2 = 3 × 10−4s−1. Direct binding of A to free Rvh can be excluded. Therefore, the state Rvh does not preexist, it is induced and only stable, as ARvh, by bound AcCh. The metastability can be described in terms of long-lived ARvh ·R1 hybrid dimers. Physiologically, the metastable hybrid may be viewed as a saving device: the functionally important, channel-active R1 conformer is, at low AcCh-concentrations [A] < 1μM, prevented to convert to the desensitized states Rh and ARvh. Furtheron, AcCh enhances the phosphorylation of phosphatidyl inositol and the auto-phosphorylation of the receptor. If the AcCh binding hysteresis causes a phosphorylation hysteresis the desensitized nAcChR may serve as a memory molecule of the transsynaptic information signalling of the neurotransmission. 相似文献
80.