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991.
Qiang Wang Yu Jiang Run Sun Prof. Dr. Xiang‐Ying Tang Prof. Dr. Min Shi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(41):14739-14745
The AuI‐catalyzed fluorination–hydration of 2‐alkynylphenol derivatives in the presence of Selectfluor [1‐chloromethyl‐4‐fluoro‐1,4‐diazoniabicyclo‐[2.2.2]octane bis(tetrafluoroborate)] has been developed. This method provides straightforward access to α‐fluorobenzofuranones with the construction of C?O, C=O, and C?F bonds in a single step on the basis of an AuI/AuIII redox catalytic cycle. Several control experiments, including the asymmetric variant of this reaction, were also conducted to gain insight into the reaction mechanism. 相似文献
992.
Dr. Lukiana L. Anka‐Lufford Kierra M. M. Huihui Dr. Nicholas J. Gower Dr. Laura K. G. Ackerman Prof. Dr. Daniel J. Weix 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(33):11564-11567
Cross‐electrophile coupling of aryl halides with alkyl halides has thus far been primarily conducted with stoichiometric metallic reductants in amide solvents. This report demonstrates that the use of tetrakis(dimethylamino)ethylene (TDAE) as an organic reductant enables the use of non‐amide solvents, such as acetonitrile or propylene oxide, for the coupling of benzyl chlorides and alkyl iodides with aryl halides. Furthermore, these conditions work for several electron‐poor heterocycles that are easily reduced by manganese. Finally, we demonstrate that TDAE addition can be used as a control element to ‘hold’ a reaction without diminishing yield or catalyst activity. 相似文献
993.
Ben Yiu‐Wing Wong Dr. Hok‐Lai Wong Yi‐Chun Wong Dr. Mei‐Yee Chan Prof. Dr. Vivian Wing‐Wah Yam 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(42):15095-15106
A series of air‐stable spiro‐fused ladder‐type boron(III) compounds has been designed, synthesized, and the electrochemistry and photophysical behavior have been characterized. By simply varying the substituents on the pyridine ring and extending the π‐conjugation of the spiro framework, the emission color of these compounds can be easily fine‐tuned spanning the visible spectrum from blue to red. All compounds exhibit a broad and structureless emission band across the entire visible region, assigned as an intramolecular charge‐transfer transition originating from the thiophene of the spiro framework to the pyridine‐borane moieties. In addition, these compounds demonstrate high photoluminescence quantum yields of up to 0.81 in dichloromethane solution and 0.86 in doped thin films. Some of the compounds have also been employed as emissive materials, in which solution‐processed organic light‐emitting devices (OLEDs) with tunable emission colors spanning the visible spectrum from blue, green to red have been realized, demonstrating the potential applications of these boron compounds in OLEDs. 相似文献
994.
Dr. Gaëlle Charron Dr. Elena Malkin Dr. Guillaume Rogez Dr. Luke J. Batchelor Dr. Sandra Mazerat Dr. Régis Guillot Dr. Nathalie Guihéry Dr. Anne‐Laure Barra Dr. Talal Mallah Dr. Hélène Bolvin 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(47):16850-16862
By using complementary experimental techniques and first‐principles theoretical calculations, magnetic anisotropy in a series of five hexacoordinated nickel(II) complexes possessing a symmetry close to C2v, has been investigated. Four complexes have the general formula [Ni(bpy)X2]n+ (bpy=2,2′‐bipyridine; X2=bpy ( 1 ), (NCS?)2 ( 2 ), C2O42? ( 3 ), NO3? ( 4 )). In the fifth complex, [Ni(HIM2‐py)2(NO3)]+ ( 5 ; HIM2‐py=2‐(2‐pyridyl)‐4,4,5,5‐tetramethyl‐4,5‐dihydro‐1H‐imidazolyl‐1‐hydroxy), which was reported previously, the two bpy bidentate ligands were replaced by HIM2‐py. Analysis of the high‐field, high‐frequency electronic paramagnetic resonance (HF‐HFEPR) spectra and magnetization data leads to the determination of the spin Hamiltonian parameters. The D parameter, corresponding to the axial magnetic anisotropy, was negative (Ising type) for the five compounds and ranged from ?1 to ?10 cm?1. First‐principles SO‐CASPT2 calculations have been performed to estimate these parameters and rationalize the experimental values. From calculations, the easy axis of magnetization is in two different directions for complexes 2 and 3 , on one hand, and 4 and 5 , on the other hand. A new method is proposed to calculate the g tensor for systems with S=1. The spin Hamiltonian parameters (D (axial), E (rhombic), and gi) are rationalized in terms of ordering of the 3 d orbitals. According to this orbital model, it can be shown that 1) the large magnetic anisotropy of 4 and 5 arises from splitting of the eg‐like orbitals and is due to the difference in the σ‐donor strength of NO3? and bpy or HIM2‐py, whereas the difference in anisotropy between the two compounds is due to splitting of the t2g‐like orbitals; and 2) the anisotropy of complexes 1 – 3 arises from the small splitting of the t2g‐like orbitals. The direction of the anisotropy axis can be rationalized by the proposed orbital model. 相似文献
995.
996.
Verónica Prado Dr. Emilio Lence Paul Thompson Prof. Alastair R. Hawkins Prof. Concepción González‐Bello 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(50):17988-18000
Shikimate kinase (SK), the fifth enzyme of the aromatic amino acid biosynthesis, is a recognized target for antibiotic drug discovery. The potential of the distinct dynamic apolar gap, which isolates the natural substrate from the solvent environment for catalysis, and the motion of Mycobacterium tuberculosis and Helicobacter pylori SK enzymes, which was observed by molecular dynamics simulations, was explored for inhibition selectivity. The results of the biochemical and computational studies reveal that the incorporation of bulky groups at position C5 of 5‐aminoshikimic acid and the natural substrate enhances the selectivity for the H. pylori enzyme due to key motion differences in the shikimic acid binding domain (mainly helix α5). These studies show that the less‐exploited motion‐based design approach not only is an alternative strategy for the development of competitive inhibitors, but could also be a way to achieve selectivity against a particular enzyme among its homologues. 相似文献
997.
998.
Yu‐Chao Yuan Hou‐Lu Liu Xu‐Bo Hu Prof. Dr. Yin Wei Prof. Dr. Min Shi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(37):13059-13063
A new visible‐light‐induced trifluoromethylation of isonitrile‐substituted methylenecyclopropanes is developed. A range of substituted 6‐(trifluoromethyl)‐7,8‐dihydrobenzo[k]phenanthridine derivatives are readily furnished by this newly developed tandem reaction with moderate to good yields. This reaction allows the direct formation of two six‐membered rings and three new C?C bonds, including the C?CF3 bond, under visible light irradiation. 相似文献
999.
1000.
Dr. Jingjun Hao Prof. Arnold L. Rheingold Marzieh Kavand Dr. Kipp J. van Schooten Prof. Christoph Boehme Dr. Marçal Capdevila‐Cortada Prof. Juan J. Novoa Eva Wöss Prof. Günther Knör Prof. Joel S. Miller 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(35):12312-12315
The reaction of 2,3,5,6‐tetracyanopyridine (TCNPy) and Cr(C6H6)2 forms diamagnetic σ‐[TCNPy]22? possessing a 1.572(3) Å intrafragment sp3–sp3 bond. This is in contrast to the structurally related 1,2,4,5‐tetracyanobenzene and 1,2,4,5‐tetracyanopyrazine that form π‐dimer dianions possessing long, multicenter bonds. 相似文献