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101.
Inside Back Cover: Intermolecular Enantioselective Dearomatization Reaction of β‐Naphthol Using meso‐Aziridine: A Bifunctional In Situ Generated Magnesium Catalyst (Angew. Chem. Int. Ed. 7/2015) 下载免费PDF全文
102.
Fragment‐Based De Novo Design Reveals a Small‐Molecule Inhibitor of Helicobacter Pylori HtrA 下载免费PDF全文
Thomas P. Schmidt Dr. Manja Böhm Katharina Stutz Daniel Reker Dr. Bernhard Pfeiffer Prof. Dr. Karl‐Heinz Altmann Prof. Dr. Steffen Backert Prof. Dr. Silja Wessler Prof. Dr. Gisbert Schneider 《Angewandte Chemie (International ed. in English)》2015,54(35):10244-10248
Sustained identification of innovative chemical entities is key for the success of chemical biology and drug discovery. We report the fragment‐based, computer‐assisted de novo design of a small molecule inhibiting Helicobacter pylori HtrA protease. Molecular binding of the designed compound to HtrA was confirmed through biophysical methods, supporting its functional activity in vitro. Hit expansion led to the identification of the currently best‐in‐class HtrA inhibitor. The results obtained reinforce the validity of ligand‐based de novo design and binding‐kinetics‐guided optimization for the efficient discovery of pioneering lead structures and prototyping drug‐like chemical probes with tailored bioactivity. 相似文献
103.
Prof. Dr. Oliver S. Wenger 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(24):6043-6052
Ruthenium complexes with polypyridine ligands are very popular choices for applications in photophysics and photochemistry, for example, in lighting, sensing, solar cells, and photoredox catalysis. There is a long-standing interest in replacing ruthenium with iron because ruthenium is rare and expensive, whereas iron is comparatively abundant and cheap. However, it is very difficult to obtain iron complexes with an electronic structure similar to that of ruthenium(II) polypyridines. The latter typically have a long-lived excited state with pronounced charge-transfer character between the ruthenium metal and ligands. These metal-to-ligand charge-transfer (MLCT) excited states can be luminescent, with typical lifetimes in the range of 100 to 1000 ns, and the electrochemical properties are drastically altered during this time. These properties make ruthenium(II) polypyridine complexes so well suited for the abovementioned applications. In iron(II) complexes, the MLCT states can be deactivated extremely rapidly (ca. 50 fs) by energetically lower lying metal-centered excited states. Luminescence is then no longer emitted, and the MLCT lifetimes become much too short for most applications. Recently, there has been substantial progress on extending the lifetimes of MLCT states in iron(II) complexes, and the first examples of luminescent iron complexes have been reported. Interestingly, these are iron(III) complexes with a completely different electronic structure than that of commonly targeted iron(II) compounds, and this could mark the beginning of a paradigm change in research into photoactive earth-abundant metal complexes. After outlining some of the fundamental challenges, key strategies used so far to enhance the photophysical and photochemical properties of iron complexes are discussed and recent conceptual breakthroughs are highlighted in this invited Concept article. 相似文献
104.
105.
Two new complexes of [Mn(2-MPyzCI)2Cl2].H2O (1) and [Mn(2-MPyzCI)2(H2O)2](NO3)2 (2) were synthesized from the reaction of MnX2.4H2O (X=Cl? and NO3?) with 2-cyanopyrazine in methanolic solution. The chelating methyl pyrazine-2-carboximidate (2-MPyzCI) ligand is formed via the methanolysis of 2-cyanopyrazine. Although coordination environment around manganes(II) ions is similar, but these complexes are different in geometrical position of 2-MPyzCI ligands. As both compounds are synthesized under the same reaction conditions, the only difference between these two complexes are counter ions and changing of geometrical position of ligands can be considered as a result of influence of the counter-anions on the molecular structures. 相似文献
106.
Dr. On Ying Yuen Dr. Chau Ming So 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(52):23644-23650
This study describes the first palladium-catalyzed, site-selective α- and γ-arylation of α,β-unsaturated ketones with (hetero)aryl halides. A wide range of hetero(aryl)halides coupled with α,β-unsaturated ketones, and transformation into the arylated products proceeded with excellent to good yields. The site selectivity of the reaction is switchable by simply changing the phosphine ligand to access either α-arylated or γ-arylated products in good to excellent yields by using a low catalyst loading, and the method demonstrates good functional-group compatibility. 相似文献
107.
Considering the importance of silylene ligands in transition metal-mediated catalytic reactions, we have scrutinized eight novel monodentate ( 1 – 4 ) and bidentate ( 1 ′ - 4 ′ ) derivatives of 2,5-diX-cyclopentasilylene-2,4-dienes (X = NH2, OH, PH2, and SH), at M06/6-311++G** level of theory. To probe the complexation ability of our scrutinized silylene ligands with Rh atom ( 1 Rh - 4 Rh and 1 ′ Rh - 4 ′ Rh , respectively), thermodynamic and structural parameters such as complexation energy (ΔECom), singlet-triplet energy gap (ΔEs-t), bond length, along with NBO and atoms in molecules analyses are provided. In going from less electron donating groups (EDGs) to more EDGs (NH2 > OH > PH2 > SH), the σ -donor strength and ligand flexibility increase. Structures 1 and 1 ′ turn out as the most nucleophilic species for showing the highest nucleophilicity (N = 5.47 and 5.40 eV, respectively). Furthermore, they exhibit the highest proton affinity values (PA = 271.46 and 271.23 kcal/mol, respectively). The results indicate that bidentate coordination mode of silylene leads to a stronger Si-Rh complex. The overall orders of σ -donation ability for monodentate and bidentate silylene ligands are 1 > 2 > 3 > 4 and 1 ′ > 2 ′ > 3 ′ > 4 ′ , respectively. 相似文献
108.
Dihydrogen Catalysis of the Reversible Formation and Cleavage of CH and NH Bonds of Aminopyridinate Ligands Bound to (η5‐C5Me5)IrIII 下载免费PDF全文
Dr. Ana Zamorano Dr. Nuria Rendón Dr. Joaquín López‐Serrano Dr. José E. V. Valpuesta Dr. Eleuterio Álvarez Prof. Dr. Ernesto Carmona 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(6):2576-2587
This study focuses on a series of cationic complexes of iridium that contain aminopyridinate (Ap) ligands bound to an (η5‐C5Me5)IrIII fragment. The new complexes have the chemical composition [Ir(Ap)(η5‐C5Me5)]+, exist in the form of two isomers ( 1+ and 2+ ) and were isolated as salts of the BArF? anion (BArF=B[3,5‐(CF3)2C6H3]4). Four Ap ligands that differ in the nature of their bulky aryl substituents at the amido nitrogen atom and pyridinic ring were employed. In the presence of H2, the electrophilicity of the IrIII centre of these complexes allows for a reversible prototropic rearrangement that changes the nature and coordination mode of the aminopyridinate ligand between the well‐known κ2‐N,N′‐bidentate binding in 1+ and the unprecedented κ‐N,η3‐pseudo‐allyl‐coordination mode in isomers 2+ through activation of a benzylic C?H bond and formal proton transfer to the amido nitrogen atom. Experimental and computational studies evidence that the overall rearrangement, which entails reversible formation and cleavage of H?H, C?H and N?H bonds, is catalysed by dihydrogen under homogeneous conditions. 相似文献
109.
Toward Functional Type III [Fe]‐Hydrogenase Biomimics for H2 Activation: Insights from Computation 下载免费PDF全文
Kevin A. Murray Dr. Matthew D. Wodrich Prof. Dr. Xile Hu Prof. Dr. Clémence Corminboeuf 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(10):3987-3996
The chemistry of [Fe]‐hydrogenase has attracted significant interest due to its ability to activate molecular hydrogen. The intriguing properties of this enzyme have prompted the synthesis of numerous small molecule mimics aimed at activating H2. Despite considerable effort, a majority of these compounds remain nonfunctional for hydrogenation reactions. By using a recently synthesized model as an entry point, seven biomimetic complexes have been examined through DFT computations to probe the influence of ligand environment on the ability of a mimic to bind and split H2. One mimic, featuring a bidentate diphosphine group incorporating an internal nitrogen base, was found to have particularly attractive energetics, prompting a study of the role played by the proton/hydride acceptor necessary to complete the catalytic cycle. Computations revealed an experimentally accessible energetic pathway involving a benzaldehyde proton/hydride acceptor and the most promising catalyst. 相似文献
110.
Hui‐Min Lin Jian‐Rong Li Chao Mu Ao Li Xu‐Feng Liu Pei‐Hua Zhao Yu‐Long Li Zhong‐Qing Jiang Hong‐Ke Wu 《应用有机金属化学》2019,33(11)
Five monophosphine‐substituted diiron propane‐1,2‐dithiolate complexes as the active site models of [FeFe]‐hydrogenases have been synthesized and characterized. Reactions of complex [Fe2(CO)6{μ‐SCH2CH(CH3)S}] ( 1 ) with a monophosphine ligand tris(4‐methylphenyl)phosphine, diphenyl‐2‐pyridylphosphine, tris(4‐chlorophenyl)phosphine, triphenylphosphine, or tris(4‐fluorophenyl)phosphine in the presence of the oxidative agent Me3NO·2H2O gave the monophosphine‐substituted diiron complexes [Fe2(CO)5(L){μ‐SCH2CH(CH3)S}] [L = P(4‐C6H4CH3)3, 2 ; Ph2P(2‐C5H4N), 3 ; P(4‐C6H4Cl)3, 4 ; PPh3, 5 ; P(4‐C6H4F)3, 6 ] in 81%–94% yields. Complexes 2 – 6 have been characterized by elemental analysis, spectroscopy, and X‐ray crystallography. In addition, electrochemical studies revealed that these complexes can catalyze the reduction of protons to H2 in the presence of HOAc. 相似文献