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991.
Lena Quambusch Ina Landel Laura Depta Jrn Weisner Niklas Uhlenbrock Matthias P. Müller Franziska Glanemann Kristina Althoff Jens T. Siveke Daniel Rauh 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(52):18999-19005
Isoforms of protein kinase Akt are involved in essential processes including cell proliferation, survival, and metabolism. However, their individual roles in health and disease have not been thoroughly evaluated. Thus, there is an urgent need for perturbation studies, preferably mediated by highly selective bioactive small molecules. Herein, we present a structure‐guided approach for the design of structurally diverse and pharmacologically beneficial covalent‐allosteric modifiers, which enabled an investigation of the isoform‐specific preferences and the important residues within the allosteric site of the different isoforms. The biochemical, cellular, and structural evaluations revealed interactions responsible for the selective binding profiles. The isoform‐selective covalent‐allosteric Akt inhibitors that emerged from this approach showed a conclusive structure–activity relationship and broke ground in the development of selective probes to delineate the isoform‐specific functions of Akt kinases. 相似文献
992.
Ludwig Hackl Dr. Alex R. Petrov Dr. Thomas Bannenberg Dr. Matthias Freytag Prof. Dr. Peter G. Jones Prof. Dr. Matthias Tamm 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(70):16148-16155
The reaction of 1,2-dipiperidinoacetylene ( 1 ) with 0.5 equivalents of SnCl2 or GeCl2⋅dioxane afforded the 1,2,3,4-tetrapiperidino-1,3-cyclobutadiene tin and germanium dichloride complexes 2 a and 2 b , respectively. A competing redox reaction was observed with excess amounts of SnCl2, which produced a tetrapiperidinocyclobutadiene dication with two trichlorostannate(II) counterions. Heating neat 1 to 110 °C for 16 h cleanly produced the dimer 1,3,4,4-tetrapiperidino-3-buten-1-yne ( 3 ); its reaction with stoichiometric amounts of SnCl2 or GeCl2⋅dioxane furnished the 1,3,4,4-tetrapiperidino-1,2-cyclobutadiene tin and germanium dichloride complexes 4 a and 4 b , respectively. Transition-metal complexes containing this novel four-membered cyclic bent allene (CBA) ligand were prepared by reaction of 3 with [(tht)AuCl], [RhCl(CO)2]2, and [(Me3N)W(CO)5] to form [(CBA)AuCl] ( 5 ), [(CBA)RhCl(CO)2] ( 6 ), and [(CBA)W(CO)5] ( 7 ). The molecular structures of all compounds 2 – 7 were determined by X-ray diffraction analyses, and density functional theory (DFT) calculations were carried out to rationalise the formation of 3 and 4 a . 相似文献
993.
Dr. Reinald Fischer Dr. Helmar Görls Philippe R. Meisinger Regina Suxdorf Prof. Dr. Matthias Westerhausen 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(55):12830-12841
Systematic variation of the 1,4-dioxane (dx) concentration during the precipitation of sparingly soluble [MgBr2(dx)2] from ethereal Grignard solutions of RMgBr has allowed the structural investigation of crystallized [R2Mg(dx)n] (n=1, 1.5, 2, and 3), which form during this dioxane method, depending on the bulkiness of R. The numbering of the complexes explored in this study is based on the number n of dioxane molecules per magnesium atom, followed by the substituent R; an apostrophe denotes coordination polymers. The following derivatives were studied by X-ray crystal-structure determination and NMR spectroscopy: n=1: [Me2Mg(μ-dx)]∞ ( 1′-Me ) and [nPr2Mg(μ-dx)]∞ ( 1′-nPr ); n=1.5: [{iPr2Mg(dx)}2(μ-dx)] ( 1.5-iPr ), [{oTol2Mg(dx)}2(μ-dx)] ( 1.5-oTol ), and [(Me3Si-C≡C)2Mg(dx)1.5]∞ ( 1.5′-C2SiMe3 ); n=2: [tBu2Mg(dx)2] ( 2-tBu ) and [oTol2Mg(dx)2] ( 2-oTol ); n=3: [Ph2Mg(dx)3] ( 3-Ph ). In the structure types 1′ , 1.5 , and 2 , the magnesium atom exhibits the coordination number 4, whereas pentacoordinate metal atoms are observed in types 3 and 1.5′ . The structure type 2′ is realized for [(Ph-C≡C)2Mg(dx)2]∞ ( 2′-C2Ph ), [MgCl2(dx)2]∞ ( 2′-Cl ), and [MgBr2(dx)2]∞ ( 2′-Br ) with hexacoordinate metal atoms. The solubility of the dioxane adducts in common organic solvents strongly depends on the degree of aggregation with the solubility decreasing from molecular to strand to layer structures. 相似文献
994.
Dr. Carsten Lenczyk Dr. Dipak Kumar Roy Kai Oberdorf Dr. Jörn Nitsch Dr. Rian D. Dewhurst Dr. Krzysztof Radacki Prof. Dr. Jean-François Halet Prof. Dr. Todd B. Marder Prof. Dr. Matthias Bickelhaupt Prof. Dr. Holger Braunschweig 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(72):16544-16549
The reactivity of a diruthenium tetrahydride complex towards three selected dihydroboranes was investigated. The use of [DurBH2] (Dur=2,3,5,6-Me4C6H) and [(Me3Si)2NBH2] led to the formation of bridging borylene complexes of the form [(Cp*RuH)2BR] (Cp*=C5Me5; 1 a : R=Dur; 1 b : R=N(SiMe3)2) through oxidative addition of the B−H bonds with concomitant hydrogen liberation. Employing the more electron-deficient dihydroborane [3,5-(CF3)2-C6H3BH2] led to the formation of an anionic complex bearing a tetraarylated chain of four boron atoms, namely Li(THF)4[(Cp*Ru)2B4H5(3,5-(CF3)2C6H3)4] ( 4 ), through an unusual, incomplete threefold dehydrocoupling process. A comparative theoretical investigation of the bonding in a simplified model of 4 and the analogous complex nido-[1,2(Cp*Ru)2(μ-H)B4H9] ( I ) indicates that there appear to be no classical σ-bonds between the boron atoms in complex I , whereas in the case of 4 the B4 chain better resembles a network of three B−B σ bonds, the central bond being significantly weaker than the other two. 相似文献
995.
Dr. Dennis Svatunek Nicole Houszka Dr. Trevor A. Hamlin Prof. Dr. F. Matthias Bickelhaupt Dr. Hannes Mikula 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(3):754-758
The strain-promoted alkyne-azide cycloaddition (SPAAC) is the most commonly employed bioorthogonal reaction with applications in a broad range of fields. Over the years, several different cyclooctyne derivatives have been developed and investigated in regard to their reactivity in SPAAC reactions with azides. However, only a few studies examined the influence of structurally diverse azides on reaction kinetics. Herein, we report our investigations of the reactivity of primary, secondary, and tertiary azides with the cyclooctynes BCN and ADIBO applying experimental and computational methods. All azides show similar reaction rates with the sterically non-demanding cyclooctyne BCN. However, due to the increased steric demand of the dibenzocyclooctyne ADIBO, the reactivity of tertiary azides drops by several orders of magnitude in comparison to primary and secondary azides. We show that this chemoselective behavior of tertiary azides can be exploited to achieve semiorthogonal dual-labeling without the need for any catalyst using SPAAC exclusively. 相似文献
996.
Xianhai Tian Lina Song Matthias Rudolph Frank Rominger Thomas Oeser A. Stephen K. Hashmi 《Angewandte Chemie (International ed. in English)》2019,58(11):3589-3593
We herein report the unprecedented synthesis of diverse biologically important aza‐heterocycles by employing sulfilimines as nitrene transfer reagents. This class of sulfur‐based aza‐ylides had not been successfully used for gold nitrene transfer before. This work contains an efficient generation of α‐imino gold carbenes by N?S cleavage of sulfilimines. These gold carbenes undergo C?H insertion, cyclopropanation, and nucleophilic attack to form indoles (44 examples), 3‐azabicyclo[3.1.0]hexan‐2‐imines (24 examples), and imidazoles (3 examples). Our study represents a unique gold‐catalyzed reaction between alkynes and sulfur ylides, and also includes the first aza‐heterocycle synthesis that proceeds by intermolecular nitrene transfer followed by cyclopropanation of the α‐imino gold carbenes. Moreover, an unexpected synthesis of 4‐acylquinolines (3 examples) from 2‐acylphenyl sulfilimines and propargylic silyl ether derivatives by a 1,2‐hydride shift onto the α‐imino gold carbene and a subsequent Mukaiyama aldol cyclization was discovered. 相似文献
997.
Fozia A. Adem Victor Kuete Armelle T. Mbaveng Matthias Heydenreich Andreas Koch Albert Ndakala 《Natural product research》2019,33(18):2609-2617
A new isoflavone, 4′-prenyloxyvigvexin A (1) and a new pterocarpan, (6aR,11aR)-3,8-dimethoxybitucarpin B (2) were isolated from the leaves of Lonchocarpus bussei and the stem bark of Lonchocarpus eriocalyx, respectively. The extract of L. bussei also gave four known isoflavones, maximaisoflavone H, 7,2′-dimethoxy-3′,4′-methylenedioxyisoflavone, 6,7,3′-trimethoxy-4′,5′-methylenedioxyisoflavone, durmillone; a chalcone, 4-hydroxylonchocarpin; a geranylated phenylpropanol, colenemol; and two known pterocarpans, (6aR,11aR)-maackiain and (6aR,11aR)-edunol. (6aR,11aR)-Edunol was also isolated from the stem bark of L. eriocalyx. The structures of the isolated compounds were elucidated by spectroscopy. The cytotoxicity of the compounds was tested by resazurin assay using drug-sensitive and multidrug-resistant cancer cell lines. Significant antiproliferative effects with IC50 values below 10 μM were observed for the isoflavones 6,7,3′-trimethoxy-4′,5′-methylenedioxyisoflavone and durmillone against leukemia CCRF-CEM cells; for the chalcone, 4-hydroxylonchocarpin and durmillone against its resistant counterpart CEM/ADR5000 cells; as well as for durmillone against the resistant breast adenocarcinoma MDA-MB231/BCRP cells and resistant gliobastoma U87MG.ΔEGFR cells. 相似文献
998.
999.
Kegler K Konieczny M Dominguez-Espinosa G Gutsche C Salomo M Kremer F Likos CN 《Physical review letters》2008,100(11):118302
Optical tweezers are employed to measure the forces of interaction within a single pair of DNA-grafted colloids, dependent on the molecular weight of the DNA chains, and the concentration and valence of the surrounding ionic medium. The resulting forces are short range and set in as the surface-to-surface distance between the colloidal cores reaches the value of the brush height. The measured force-distance relation is analyzed by means of a theoretical treatment that quantitatively describes the effects of compression of the chains on the surface of the opposite-lying colloid. Quantitative agreement with the experiment is obtained for all parameter combinations. 相似文献
1000.
We study dc charge and spin transport through a weakly coupled quantum dot, driven by a nonadiabatic periodic change of system parameters. We generalize the model of Tien and Gordon to simultaneously oscillating voltages and tunnel couplings. When applying our general result to the two-parameter charge pumping in quantum dots, we find interference effects between the oscillations of the voltage and tunnel couplings. We show that these interference effects may explain recent measurements in metallic islands. Furthermore, we discuss the possibility to electrically pump a spin current in presence of a static magnetic field. 相似文献