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101.
Gunasekaran Balamurugan Sundarraman Balaji Rengan Ramesh Nattamai S.P. Bhuvanesh 《应用有机金属化学》2019,33(1)
A panel of six new arene Ru (II)‐NHC complexes 2a‐f , (NHC = 1,3‐diethyl‐(5,6‐dimethyl)benzimidazolin‐2‐ylidene 1a , 1,3‐dicyclohexylmethyl‐(5,6‐dimethyl)benzimidazolin‐2‐ylidene 1b and 1,3‐dibenzyl‐(5,6‐dimethyl)benzimidazolin‐2‐ylidene 1c ) were synthesized from the transmetallation reaction of Ag‐NHC with [(η6‐arene)RuCl2]2 and characterized. The ruthenium (II)‐NHC complexes 2a‐f were developed as effective catalysts for α‐alkylation of ketones and synthesis of bioactive quinoline using primary/amino alcohols as coupling partners respectively. The reactions were performed with 0.5 mol% catalyst load in 8 h under aerobic condition and the maximum yield was up to 96%. Besides, the different alkyl wingtips on NHC and arene moieties were studied to differentiate the catalytic robustness of the complexes in the transformations. 相似文献
102.
Pan Huang Dawen Xu Robert M. Reich Felix Kaiser Boping Liu Fritz E. Kühn 《Tetrahedron letters》2019,60(24):1574-1577
A first example of an Et2Zn mediated silylation of 1-aklynes is reported. A series of functional groups are tolerated in this reaction. Mechanistic studies support Zn alkynilides as intermediates in the reaction. This reaction protocol provides a practical method for the preparation of alkynylsilanes and expands the application of organometallic zinc in organic synthesis. 相似文献
103.
Since the late seventies, the search for new molecular receptors has been constant in perfecting the affinity and selectivity of recognition in different media. At present, a renewed interest in (host:guest) chemistry focuses on the molecular detection of specific targets such as biological, pollutant, toxic or explosive species. This review of triphenylene-based receptors outlines their recent contribution to molecular recognition. Two main structural approaches were investigated to transform a simple triphenylene moiety into a host for neutral aromatic compounds or cations, by tailoring multivalent molecules provided with or without a flatten cavity. The properties of different receptors are presented along with the latest synthetic methods to prepare high-value triphenylenes and the perspectives in the field of sensing. In addition, the role of functionalized triphenylenes in extended (host:guest) systems is illustrated by the main examples of discotic liquid crystals and porous coordination polymers involving this polyaromatic compound. 相似文献
104.
Denis D. Borisov Grigory R. Chermashentsev Roman A. Novikov Yury V. Tomilov 《Tetrahedron letters》2019,60(10):746-750
New “four-component” self-assembly of polyaromatic thiophene structures based on styrylmalonates and 5-phenylthiophene-2-carbaldehyde has been developed. This process is promoted by GaCl3 and involves two [2?+?3]-annulation steps on the CHO-groups and para-substitution into one Ph-ring. The main feature of discovered process is a high diastereoselectivity with a significant increase in molecular complexity. The resulting polyaromatic structures containing two thiophene moieties in each structure have intense color and strong absorption in a near UV spectral region with absorption maxima in the range of 257–360?nm. 相似文献
105.
In this work, low‐moisture glycidyl azide polymer (GAP) was successfully prepared using a modified two‐step method. The modified method resembles the structure of the classical two‐step method, which is widely used to prepare the GAP. Firstly, epichlorohydrin (ECH) is polymerized into polyepicholorohydrin (PECH), which is subjected afterward to azidation step using sodium azide (NaN3). Interestingly, minimizing the water content in the final GAP product, which is a challenging when dealing with GAP as a rocket propellant binder, was effectively achieved by utilizing low boiling point solvents instead of the relatively high boiling point Dimethyl formamide (DMF), monitoring the volatility of ECH and controlling the exothermicity of the reaction. Prepared GAP samples were investigated using Fourier transformer infra‐red (FT‐IR), gel‐permeation chromatography (GPC) and elemental analysis apparatus (CHNS) were used to characterize the product. The moisture % in the final product was examined using the Karl‐Fisher Technique. Results showed the successful preparation of GAP with low water content (<0.01 %), high average molecular weight (> 2000 g · mol–1), 42.82 % nitrogen, a viscosity of 3484 cP at 20 °C, yield ranges between 95–98 % and a polydispersity index of 1.2. The prepared GAP is promising for replacement of the classical GAPs in the energetic materials applications. 相似文献
106.
107.
Eva Rivera‐Chao Maider Mitxelena Jesús A. Varela Martín Faans‐Mastral 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(50):18398-18402
The first copper‐catalyzed enantioselective allylboration of alkynes is reported. The method employs a multitasking chiral NHC‐Cu catalyst and provides access to densely functionalized molecules from simple starting materials with excellent levels of chemo‐, regio‐, and enantioselectivity. These multifunctional products display highly versatile reactivity as shown by the synthesis of a variety of non‐racemic molecular scaffolds. DFT calculations were conducted to gain insight into the high selectivity levels of this catalytic process. 相似文献
108.
Fan Yang Shuaishuai Zhang Jingpeng Song Qing Du Guixiang Li Nadezda V. Tarakina Markus Antonietti 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(52):18989-18992
Artificial humic acids (A‐HA) made from biomass in a hydrothermal process turn otherwise highly insoluble phosphates (e.g. iron phosphate as a model) into highly available phosphorus, which contributes to the fertility of soils and the coupled plant growth. A detailed electron microscopy study revealed etching of the primary iron phosphate crystals by the ‐COOH and phenolic groups of humic acids, but also illustrated the importance of the redox properties of humic matter on the nanoscale. The combined effects result in the formation of then bioavailable phosphate nanoparticles stabilized by humic matter. Typical agricultural chemical tests indicate that the content of total P and directly plant‐available P improved largely. Comparative pot planting experiments before and after treatment of phosphates with A‐HA demonstrate significantly enhanced plant growth, as quantified in higher aboveground and belowground plant biomass. 相似文献
109.
Hans Jagusch Markus Werner Oliver Werz Georg Pohnert 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(49):17805-17809
Arachidonic‐acid‐derived prostaglandins (PGs), specifically PGE2, play a central role in inflammation and numerous immunological reactions. The enzymes of PGE2 biosynthesis are important pharmacological targets for anti‐inflammatory drugs. Besides mammals, certain edible marine algae possess a comprehensive repertoire of bioactive arachidonic‐acid‐derived oxylipins including PGs that may account for food poisoning. Described here is the analysis of PGE2 biosynthesis in the red macroalga Gracilaria vermiculophylla that led to the identification of 15‐hydroperoxy‐PGE2, a novel precursor of PGE2 and 15‐keto‐PGE2. Interestingly, this novel precursor is also produced in human macrophages where it represents a key metabolite in an alternative biosynthetic PGE2 pathway in addition to the well‐established arachidonic acid‐PGG2‐PGH2‐PGE2 route. This alternative pathway of mammalian PGE2 biosynthesis may open novel opportunities to intervene with inflammation‐related diseases. 相似文献
110.
建立了一种细胞趋硬性迁移的理论模型和有限元分析框架,为连续变刚度人工基质的试验设计提供理论依据。考虑了细胞体的黏弹性属性,以及细胞与基质间的配受体动态反应过程,并以配受体合成时间为时间步长,将细胞运动方程化为静力学形式进行求解。对有限元过程提出一种动约束,便于消除其结构矩阵的奇异性。结果表明,模型能够模拟黏着斑内部力的快速波动现象,细胞的运动速度与观测数据一致,可有效模拟20,h以上的长时程问题。 相似文献