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991.
Versatile Iridicycle Catalysts for Highly Efficient and Chemoselective Transfer Hydrogenation of Carbonyl Compounds in Water 下载免费PDF全文
Dinesh Talwar Dr. Xiaofeng Wu Dr. Ourida Saidi Noemí Poyatos Salguero Prof. Jianliang Xiao 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(40):12835-12842
Cyclometalated iridium complexes are shown to be highly efficient and chemoselective catalysts for the transfer hydrogenation of a wide range of carbonyl groups with formic acid in water. Examples include α‐substituted ketones (α‐ether, α‐halo, α‐hydroxy, α‐amino, α‐nitrile or α‐ester), α‐keto esters, β‐keto esters and α,β‐unsaturated aldehydes. The reduction was carried out at substrate/catalyst ratios of up to 50 000 at pH 4.5 and required no organic solvent. The protocol provides a practical, easy and efficient way for the synthesis of β‐functionalised secondary alcohols, such as β‐hydroxyethers, β‐hydroxyamines and β‐hydroxyhalo compounds, which are valuable intermediates in pharmaceutical, fine chemical, perfume and agrochemical synthesis. 相似文献
992.
Yuya Ikeuchi Dr. Hiroshi Takatsu Dr. Cédric Tassel Yoshihiro Goto Taito Murakami Prof. Hiroshi Kageyama 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2017,129(21):5864-5867
A high-pressure reaction yielded the fully occupied tetragonal tungsten bronze K3W5O15 (K0.6WO3). The terminal phase shows an unusual transport property featuring slightly negative temperature-dependence in resistivity (dρ/dT<0) and a large Wilson ratio of RW=3.2. Such anomalous metallic behavior possibly arises from the low-dimensional electronic structure with a van Hove singularity at the Fermi level and/or from enhanced magnetic fluctuations by geometrical frustration of the tungsten sublattice. The asymmetric nature of the tetragonal tungsten bronze KxWO3-K0.6−yBayWO3 phase diagram implies that superconductivity for x≤0.45 originates from the lattice instability because of potassium deficiency. A cubic perovskite KWO3 phase was also identified as a line phase—in marked contrast to NaxWO3 and LixWO3 with varying quantities of x (<1). This study presents a versatile method by which the solubility limit of tungsten bronze oxides can be extended. 相似文献
993.
Dr. Qiang-Shuai Gu Prof. Dan Yang 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2017,129(21):5980-5983
The mitomycins, a family of bioactive natural products, feature a compact 6/5/5-fused polycyclic ring structure densely decorated with highly reactive and/or fragile quinone, amino ketal, and aziridine as well as carbamate moieties. It is this striking feature that has defeated numerous synthetic attempts towards these apparently small molecules, rendering them one of the most formidable targets for total synthesis. We herein report the first enantioselective synthesis of (+)-mitomycin K, a representative of G series mitomycins. The key step of this synthesis is an enantioselective oxidative cyclization catalyzed by a palladium/(+)-sparteine system that had previously been developed by our group. The robustness of this method bodes well for further applications in the asymmetric total synthesis of natural products, particularly those with characteristic 6/5/5-fused pyrroloindole skeletons. 相似文献
994.
Prof. Dr. Jörg Grunenberg 《Angewandte Chemie (International ed. in English)》2017,56(25):7288-7291
The first quantum-mechanical calculations of all relevant potential constants in both the iron-molybdenum cofactor and the iron-vanadium cofactor of nitrogenase suggest that the carbide is bound to the center of the enzyme much more strongly than hitherto assumed. Previous studies seemed to indicate a dummy function of the interstitial carbon, with a weak force constant (ca. 0.32 N cm−1). Our new investigations confirm a different picture: the central carbon atom binds the iron-sulfur cluster through six covalent C−Fe bonds. With a potential constant of more than 1.3 N cm−1, the interstitial carbon also appears to be dynamically persistent. According to our investigations, the values for the elasticity within the iron-sulfur cluster have to be corrected too. These new details on the mechano-chemical properties of the FeMo cofactor will be important for elucidating the catalytic cycle of nitrogen fixation. By implementing our new algorithm in the freely available COMPLIANCE program, the dependence on the coordinates during the calculation of Hesse matrices is eliminated completely. 相似文献
995.
Dr. Lydia M. Peschel Carina Vidovič Dr. Ferdinand Belaj Dr. Dmytro Neshchadin Prof. Nadia C. Mösch-Zanetti 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(15):3893-3902
The synthesis and structural determination of four tungsten alkyne complexes coordinated by the bio-inspired S,N-donor ligand 2-(4′,4′-dimethyloxazoline-2′-yl)thiophenolate (S-Phoz) is presented. A previously established protocol that involved the reaction of the respective alkyne with the bis-carbonyl precursor [W(CO)2(S-Phoz)2] was used for the complexes [W(CO)(C2R2)(S-Phoz)2] (R=H, 1 a ; Me, 1 b ; Ph, 1 c ). Oxidation with pyridine-N-oxide gave the corresponding W-oxo species [WO(C2R2)(S-Phoz)2] (R=H, 2 a ; Me, 2 b ; Ph, 2 c ). All W-oxo-alkyne complexes ( 2 a , b , c ) were found to be capable of alkyne release upon light irradiation to afford five-coordinate [WO(S-Phoz)2] ( 3 ). The photoinduced release of the alkyne ligand was studied in detail by in situ 1H NMR measurements, which revealed correlation of the photodissociation rate constant ( 2 b>2 a>2 c ) with the elongation of the alkyne C≡C bond in the molecular structures. Oxidation of [WO(S-Phoz)2] ( 3 ) with pyridine-N-oxide yielded [WO2(S-Phoz)2] ( 4 ), which shows highly fluxional behavior in solution. Variable-temperature 1H NMR spectroscopy revealed three isomeric forms with respect to the ligand arrangement versus each other. Furthermore, compound 4 rearranges to tetranuclear oxo compound [W4O4(μ-O)6(S-Phoz)4] ( 5 ) and dinuclear [{WO(μ-O)(S-Phoz)}2] ( 6 ) over time. The latter two were identified by single-crystal X-ray diffraction analyses. 相似文献
996.
Dr. Philipp Le Dr. Matthew B. Nodwell Dr. Jürgen Eirich Prof. Stephan A. Sieber 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(54):12644-12651
The illudin natural product family are fungal secondary metabolites with a characteristic spirocyclopropyl-substituted fused 6,5-bicyclic ring system. They have been extensively studied for their cytotoxicity in various tumor cell types, and semisynthetic derivatives with improved therapeutic characteristics have progressed to clinical trials. Although it is believed that this potent alkylating compound class acts mainly through DNA modification, little is known about its binding to protein sites in a cellular context. To reveal putative protein targets of the illudin family in live cancer cells, we employed a semisynthetic strategy to access a series of illudin-based probes for activity-based protein profiling (ABPP). While the probes largely retained potent cytotoxicity, proteomic profiling studies unraveled multiple protein hits, suggesting that illudins exert their mode of action not from addressing a specific protein target but rather from DNA modification and unselective protein binding. 相似文献
997.
Xueying Jia Prof. Dr. Carsten Streb Prof. Dr. Yu-Fei Song 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(68):15548-15554
Polyoxometalates (POMs) are promising catalysts for the electrochemical hydrogen production from water owing to their high intrinsic catalytic activity and chemical tunability. However, poor electrical conductivity and easy detachment of the POMs from the electrode cause significant challenges under operating condition. Herein, a simple one-step hydrothermal method is reported to synthesize a series of Dexter–Silverton POM/Ni foam composites (denoted as Ni M -POM/Ni; M =Co, Zn, Mn), in which the stable linkage between the POM catalysts and the Ni foam electrodes lead to high activity for the hydrogen evolution reaction (HER). Among them, the highest HER performance can be observed in the NiCo-POM/Ni, featuring an overpotential of 64 mV (at 10 mA cm−2, vs. reversible hydrogen electrode), and a Tafel slope of 75 mV dec−1 in 1.0 m aqueous KOH. Moreover, the NiCo-POM/Ni catalyst showed a high faradaic efficiency ≈97 % for HER. Post-catalytic of NiCo-POM/Ni analyses showed virtually no mechanical or chemical degradation. The findings propose a facile and inexpensive method to design stable and effective POM-based catalysts for HER in alkaline water electrolysis. 相似文献
998.
Dr. Nicolai Wagner Milena Schuhmacher Annett Lohmann Dr. André Nadler 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(68):15483-15487
Photorelease of caged compounds is among the most powerful experimental approaches for studying cellular functions on fast timescales. However, its full potential has yet to be exploited, as the number of caged small molecules available for cell biological studies has been limited by synthetic challenges. Addressing this problem, a straightforward, one-step procedure for efficiently synthesizing caged compounds was developed. An in situ generated benzylic coumarin triflate reagent was used to specifically functionalize carboxylate and phosphate moieties in the presence of free hydroxy groups, generating various caged lipid metabolites, including a number of GPCR ligands. By combining the photo-caged ligands with the respective receptors, an easily implementable experimental platform for the optical control and analysis of GPCR-mediated signal transduction in living cells was developed. Ultimately, the described synthetic strategy allows rapid generation of photo-caged small molecules and thus greatly facilitates the analysis of their biological roles in live cell microscopy assays. 相似文献
999.
Tatsuya Sakakura Assoc. Prof. Naoya Murakami Dr. Yoshiyuki Takatsuji Masayuki Morimoto Prof. Tetsuya Haruyama 《Chemphyschem》2019,20(11):1467-1474
Electric-discharge nitrogen comprises three main types of excited nitrogen species-atomic nitrogen (Natom), excited nitrogen molecules (N2*), and nitrogen ions (N2+) – which have different lifetimes and reactivities. In particular, the interfacial reaction locus between the discharged nitrogen and the water phase produces nitrogen compounds such as ammonia and nitrate ions (denoted as N-compounds generically); this is referred to as the plasma/liquid interfacial (P/L) reaction. The Natom amount was analyzed quantitatively to clarify the contribution of Natom to the P/L reaction. We focused on the quantitative relationship between Natom and the produced N-compounds, and found that both N2* and N2+, which are active species other than Natom, contributed to P/L reaction. The production of N-compounds from N2* and N2+ was enhanced upon UV irradiation of the water phase, but the production of N-compounds from Natom did not increase by UV irradiation. These results revealed that the P/L reactions starting from Natom and those starting from N2* and N2+ follow different mechanisms. 相似文献