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61.
Lars J. Wesenberg Erika Diehl Till J. B. Zähringer Carolin Dörr Dr. Dieter Schollmeyer Dr. Akihiro Shimizu Prof. Dr. Jun-ichi Yoshida Prof. Dr. Ute A. Hellmich Prof. Dr. Siegfried R. Waldvogel 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(72):17574-17580
The efficient production of many medicinally or synthetically important starting materials suffers from wasteful or toxic precursors for the synthesis. In particular, the aromatic non-protected primary amine function represents a versatile synthetic precursor, but its synthesis typically requires toxic oxidizing agents and transition metal catalysts. The twofold electrochemical amination of activated benzene derivatives via Zincke intermediates provides an alternative sustainable strategy for the formation of new C−N bonds of high synthetic value. As a proof of concept, we use our approach to generate a benzoxazinone scaffold that gained attention as a starting structure against castrate-resistant prostate cancer. Further improvement of the structure led to significantly increased cancer cell line toxicity. Thus, exploiting environmentally benign electrooxidation, we present a new versatile and powerful method based on direct C−H activation that is applicable for example the production of medicinally relevant compounds. 相似文献
62.
Frederick MT Achtyl JL Knowles KE Weiss EA Geiger FM 《Journal of the American Chemical Society》2011,133(19):7476-7481
This Article reports measurements of the intra- and intermolecular ordering of tight-binding octylphosphonate ligands on the surface of colloidal CdSe quantum dots (QDs) within solid state films, and the dependence of this order on the size of the QDs. The order of the organic ligands, as probed by vibrational sum frequency generation (SFG) spectroscopy, decreases as the radius of the QDs decreases; this decrease is correlated with a decrease in the order of underlying Cd(2+), as detected by X-ray photoelectron spectroscopy (XPS) line width measurements, for radii of the QDs, R > 2.4 nm, and is independent of the disorder of the Cd(2+) for R < 2.4 nm. We believe that, for R < 2.4, the decreasing order of the ligands with decreasing size is due to an increase in the curvature of the QD surfaces. Disorder in the Cd(2+) results from the presence of a shell of Cd(2+)-surfactant complexes that form during synthesis, so this work demonstrates the possibility for chemical control over molecular order within films of colloidal QDs by changing the surfactant mixture. 相似文献
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We propose an adaptive hybrid method suitable for stochastic simulation of diffusion dominated reaction–diffusion processes. For such systems, simulation of the diffusion requires the predominant part of the computing time. In order to reduce the computational work, the diffusion in parts of the domain is treated macroscopically, in other parts with the tau-leap method and in the remaining parts with Gillespie’s stochastic simulation algorithm (SSA) as implemented in the next subvolume method (NSM). The chemical reactions are handled by SSA everywhere in the computational domain. A trajectory of the process is advanced in time by an operator splitting technique and the timesteps are chosen adaptively. The spatial adaptation is based on estimates of the errors in the tau-leap method and the macroscopic diffusion. The accuracy and efficiency of the method are demonstrated in examples from molecular biology where the domain is discretized by unstructured meshes. 相似文献
66.
Zeynep Güven Lars Denker Hadi Dolati Daniela Wullschläger Dr. Bartosz Trzaskowski Dr. René Frank 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(32):e202200673
Donor-acceptor cyclopropanes or cyclobutanes are dipolar reagents, which are widely used in the synthesis of complex organic (hetero)cycles in ring expansion reactions. Applying this concept to boron containing heterocycles, the four-membered borete cyclo-iPr2N-BC10H6 reacted with the carbon donor ligands 2,6-xylylisonitrile and the carbene IMes :C(NMesCH)2 with ring expansion and ring fusion, respectively. In particular, the tetracyclic structure formed with IMes displays zwitterionic character and absorption in the visible region. In contrast to the carbene IMes, the heavier carbenoids :Si(NDippCH)2 and :Ga(AmIm) with a two-coordinate donor atom afford spiro-type bicyclic compounds, which display four-coordinate geometry at silicon or gallium. (TD-)DFT calculations provide deeper insight into the mechanism of formation and the absorption properties of these new compounds. 相似文献
67.
Dr. Ramasamy Jayarajan Tautvydas Kireilis Prof. Lars Eriksson Prof. Kálmán J. Szabó 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(58):e202202059
A broad range of aliphatic, aromatic, and heterocyclic boronic acids were successfully homologated using trifluorodiazoethane in the presence of BINOL derivatives to provide the corresponding chiral trifluoromethyl containing boronic acid derivatives in high yields and excellent enantioselectivity. The in situ conversion of the chiral transient boronic acids to the corresponding alcohols or β-CF3 carboxylates are also demonstrated. 相似文献
68.
Lars Rummel Jan M. Schümann Prof. Dr. Peter R. Schreiner 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(55):13699-13702
We present a computational analysis of hexaphenylethane derivatives with heavier tetrels comprising the central bond. In stark contrast to parent hexaphenylethane, the heavier tetrel derivatives can readily be prepared. In order to determine the origin of their apparent thermodynamic stability against dissociation as compared to the carbon case, we employed local energy decomposition analysis (LED) and symmetry-adapted perturbation theory (SAPT) at the DLPNO-CCSD(T)/def2-TZVP and sSAPT0/def2-TZVP levels of theory. We identified London dispersion (LD) interactions as the decisive factor for the molecular stability of heavier tetrel derivatives. This stability is made possible owing to the longer (than C−C) central bonds that move the phenyl groups out of the heavily repulsive regime so they can optimally benefit from LD interactions. 相似文献
69.
Dr. Dominik Raiser Dr. Klaus Eichele Dr. Hartmut Schubert Prof. Dr. Lars Wesemann 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(56):14073-14080
The reaction of the intramolecular germylene-phosphine Lewis pair (o-PPh2)C6H4GeAr* ( 1 ) with Group 15 element trichlorides ECl3 (E=P, As, Sb) was investigated. After oxidative addition, the resulting compounds (o-PPh2)C6H4(Ar*)Ge(Cl)ECl2 ( 2 : E=P, 3 : E=As, 4 : E=Sb) were reduced by using sodium metal or LiHBEt3. The molecular structures of the phosphine-stabilized phosphinidene (o-PPh2)C6H4(Ar*)Ge(Cl)P ( 5 ), arsinidene (o-PPh2)C6H4(Ar*)Ge(Cl)As ( 6 ) and stibinidene (o-PPh2)C6H4(Ar*)Ge(Cl)Sb ( 7 ) are presented; they feature a two-coordinate low-valent Group 15 element. After chloride abstraction, a cyclic germaphosphene [(o-PPh2)C6H4(Ar*)GeP] [B(C6H3(CF3)2)4] ( 8 ) was isolated. The 31P NMR data of the germaphosphene were compared with literature examples and analyzed by quantum chemical calculations. The phosphinidene was treated with [iBu2AlH]2, and the product of an Al−H addition to the low-valent phosphorus atom (o-PPh2)C6H4(Ar*)Ge(H)P(H)Al(C4H9)2 ( 9 ) was characterized. 相似文献
70.
Dominik Raiser Dr. Hartmut Schubert Prof. Dr. Holger F. Bettinger Prof. Dr. Lars Wesemann 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(6):1981-1983
Halide and phenyl substituted germaborenes were shown to react with azides at room temperature and transfer a borylene moiety to give iminoboranes. This iminoborane synthesis based on a borylene transfer route was investigated computationally in the case of the phenyl substituted germaborene. 相似文献