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941.
Enantioselective Synthesis of Quaternary Carbon Stereocenters: Addition of 3‐Substituted Oxindoles to Vinyl Sulfone Catalyzed by Pentanidiums
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Dr. Lili Zong Shubo Du Kek Foo Chin Dr. Chao Wang Prof. Dr. Choon‐Hong Tan 《Angewandte Chemie (International ed. in English)》2015,54(32):9390-9393
A pentanidium‐catalyzed highly enantioselective conjugate addition of 3‐alkyloxindoles to phenyl vinyl sulfone has been demonstrated. This approach allows the construction of 3,3‐dialkyl‐substituted oxindole frameworks with high yield and excellent enantioselectivity (up to 99 %) under simple phase‐transfer conditions. A variety of oxindoles bearing all‐carbon quaternary stereogenic centers were obtained in the presence of 0.25 mol % pentanidium. Meanwhile, practicality was illustrated by a gram‐scale asymmetric synthesis of two 3,3‐dialkyl‐substituted oxindoles. The resulting adduct can be smoothly transformed to the natural product analogue in a short synthetic route. 相似文献
942.
Corrigendum: Crowdsourcing Natural Products Discovery to Access Uncharted Dimensions of Fungal Metabolite Diversity
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943.
A Two‐Coordinate Cobalt(II) Imido Complex with NHC Ligation: Synthesis,Structure, and Reactivity
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Jingzhen Du Linbo Wang Prof. Dr. Meihua Xie Prof. Dr. Liang Deng 《Angewandte Chemie (International ed. in English)》2015,54(43):12640-12644
The synthesis, structural characterization, and reactivity of the first two‐coordinate cobalt complex featuring a metal–element multiple bond [(IPr)Co(NDmp)] ( 4 ; IPr=1,3‐bis(2′,6′‐diisopropylphenyl)imidazole‐2‐ylidene; Dmp=2,6‐dimesitylphenyl) is reported. Complex 4 was prepared from the reaction of [(IPr)Co(η2‐vtms)2] (vtms=vinyltrimethylsilane) with DmpN3. An X‐ray diffraction study revealed its linear C? Co? N core and a short Co? N distance (1.691(6) Å). Spectroscopic characterization and calculation studies indicated the high‐spin nature of 4 and the multiple‐bond character of the Co? N bond. Complex 4 effected group‐transfer reactions to CO and ethylene to form isocyanide and imine, respectively. It also facilitated E? H (E=C, Si) σ‐bond activation of terminal alkyne and hydrosilanes to produce the corresponding cobalt(II) alkynyl and cobalt(II) hydride complexes as 1,2‐addition products. 相似文献
944.
945.
Jialei Du Prof. Zuofeng Chen Dr. Shengrong Ye Prof. Benjamin J. Wiley Prof. Thomas J. Meyer 《Angewandte Chemie (International ed. in English)》2015,54(7):2073-2078
Copper metal is in theory a viable oxidative electrocatalyst based on surface oxidation to CuIII and/or CuIV, but its use in water oxidation has been impeded by anodic corrosion. The in situ formation of an efficient interfacial oxygen‐evolving Cu catalyst from CuII in concentrated carbonate solutions is presented. The catalyst necessitates use of dissolved CuII and accesses the higher oxidation states prior to decompostion to form an active surface film, which is limited by solution conditions. This observation and restriction led to the exploration of ways to use surface‐protected Cu metal as a robust electrocatalyst for water oxidation. Formation of a compact film of CuO on Cu surface prevents anodic corrosion and results in sustained catalytic water oxidation. The Cu/CuO surface stabilization was also applied to Cu nanowire films, which are transparent and flexible electrocatalysts for water oxidation and are an attractive alternative to ITO‐supported catalysts for photoelectrochemical applications. 相似文献
946.
A Highly cis‐Selective and Enantioselective Metal‐Free Hydrogenation of 2,3‐Disubstituted Quinoxalines
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Zhenhua Zhang Prof. Dr. Haifeng Du 《Angewandte Chemie (International ed. in English)》2015,54(2):623-626
A wide range of 2,3‐disubstituted quinoxalines have been successfully hydrogenated with H2 using borane catalysts to produce the desired tetrahydroquinoxalines in 80–99 % yields with excellent cis selectivity. Significantly, the asymmetric reaction employing chiral borane catalysts generated by the in situ hydroboration of chiral dienes with HB(C6F5)2 under mild reaction conditions has also been achieved with up to 96 % ee, and represents the first catalytic asymmetric system to furnish optically active cis‐2,3‐disubstituted 1,2,3,4‐tetrahydroquinoxalines. 相似文献
947.
Direct Insight into the Three‐Dimensional Internal Morphology of Solid–Liquid–Vapor Interfaces at Microscale
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Dr. Shuai Yang Jiexing Du Dr. Moyuan Cao Dr. Xi Yao Dr. Jie Ju Dr. Xu Jin Prof. Bin Su Prof. Kesong Liu Prof. Lei Jiang 《Angewandte Chemie (International ed. in English)》2015,54(16):4792-4795
Solid–liquid–vapor interfaces dominated by the three‐phase contact line, usually performing as the active center in reactions, are important in biological and industrial processes. In this contribution, we provide direct three‐dimensional (3D) experimental evidence for the inside morphology of interfaces with either Cassie or Wenzel states at micron level using X‐ray micro‐computed tomography, which allows us to accurately “see inside” the morphological structures and quantitatively visualize their internal 3D fine structures and phases in intact samples. Furthermore, the in‐depth measurements revealed that the liquid randomly and partly located on the top of protrusions on the natural and artificial superhydrophobic surfaces in Cassie regime, resulting from thermodynamically optimal minimization of the surface energy. These new findings are useful for the optimization of classical wetting theories and models, which should promote the surface scientific and technological developments. 相似文献
948.
Direct Conversion of Bulk Metals to Size‐Tailored,Monodisperse Spherical Non‐Coinage‐Metal Nanocrystals
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Rui‐Chun Luo Chao Li Prof. Xi‐Wen Du Prof. Jing Yang 《Angewandte Chemie (International ed. in English)》2015,54(16):4787-4791
Monodisperse non‐noble metal nanocrystals (NCs) that are highly uniform in shapes and particle size are much desired in various advanced applications, and are commonly prepared by either thermal decomposition or reduction, where reactive organometallic precursors or/and strong reducing agents are mandatory; however, these are usually toxic, costly, or suffer a lack of availability. Bulk Group 12 metals can now be converted into ligand‐protected, highly crystalline, monodisperse spherical metal NCs with precisely controlled sizes without using any precursors and reducers. The method is based on low‐power NIR‐laser‐induced size‐selective layer‐by‐layer surface vaporization. The monodisperse Cd NCs show pronounced deep‐UV (DUV) localized surface plasmon resonance making them highly competitive DUV‐plasmonic materials. This approach will promote appreciably the emergence of a wide range of monodisperse technically important non‐coinage metal NCs with compelling functionalities. 相似文献
949.
Teng‐Shuo Zhang Rui Du Yan‐Yin Zhao Jia‐Dan Xue Hui‐Gang Wang Xuming Zheng 《Journal of Raman spectroscopy : JRS》2016,47(3):299-309
The B‐band resonance Raman spectra of 2(1H)‐pyridinone (NHP) in water and acetonitrile were obtained, and their intensity patterns were found to be significantly different. To explore the underlying excited state tautomeric reaction mechanisms of NHP in water and acetonitrile, the vibrational analysis was carried out for NHP, 2(1D)‐pyridinone (NDP), NHP–(H2O)n (n = 1, 2) clusters, and NDP–(D2O)n (n = 1, 2) clusters on the basis of the FT‐Raman experiments, the B3LYP/6‐311++G(d,p) computations using PCM solvent model, and the normal mode analysis. Good agreements between experimental and theoretically predicted frequencies and intensities in different surrounding environments enabled reliable assignments of Raman bands in both the FT‐Raman and the resonance Raman spectra. The results indicated that most of the B‐band resonance Raman spectra in H2O was assignable to the fundamental, overtones, and combination bands of about ten vibration modes of ring‐type NHP–(H2O)2 cluster, while most of the B‐band resonance Raman spectra in CH3CN was assigned to the fundamental, overtones, and combination bands of about eight vibration modes of linear‐type NHP–CH3CN. The solvent effect of the excited state enol‐keto tautomeric reaction mechanisms was explored on the basis of the significant difference in the short‐time structural dynamics of NHP in H2O and CH3CN. The inter‐molecular and intra‐molecular ESPT reaction mechanisms were proposed respectively to explain the Franck–Condon region structural dynamics of NHP in H2O and CH3CN.Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
950.
Cheng-Fang Wang Li Fan Mei Tian Shu-Shan Du Zhi-Wei Deng Jiang-Bin Feng 《Natural product research》2015,29(14):1380-1383
This work aimed to investigate benzophenanthridine from the roots of Zanthoxylum nitidum (Roxb.) DC. var. fastuosum How ex Huang for the first time. Thirteen benzophenanthridines were isolated, and our results of the cytotoxic activities indicated that compound 6 exhibited the best potency against A549, Hela, SMMC-7721 and EJ, with the IC50 values of 27.50, 37.50, 16.95 and 60.42 μM, respectively. Compounds 7 and 11 also showed strong cytotoxicity when tested against the four human cancer cell lines (A549, Hela, SMMC-7721 and EJ), while only compounds 12 and 13 displayed cytotoxicity in inhibiting BALL-1 proliferation among all the compounds. These results suggested that benzophenanthridines may become a valid alternative of potential basis for new anti-proliferative agents. 相似文献