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Hui Mei Wenjia Han Jianglin Hu Se Xiao Yizhu Lei Rui Zhang Wanlin Mo Guangxing Li 《应用有机金属化学》2013,27(3):177-183
This work describes a highly efficient unstrained C(sp3)―N bond activation approach for synthesis of N,N‐dimethylacetamide (DMAc) via catalytic carbonylation of trimethylamine using a PdCl2/bipy (bipy = 2,2′‐bipyridine)/Me4NI catalyst system. A low Pd catalyst dosage (1.0 mol%) is sufficient for high selectivity (98.1%) and yield (90.8%), with a turnover number (TON) of 90.0 mmol of DMAc obtained per mmol of PdCl2 employed under mild reaction conditions. The influence of reaction parameters such as catalyst precursor dosage, ligand type and promoter on activity is investigated. This work also discusses in detail the halide promoter's role in the reaction, and provides a plausible mechanism based on the intermediates methyl iodide and acetyl iodide. Analyses indicate that the carbonylation of trimethylamine may proceed through an active intermediate acetyl iodide formed by carbonylation of methyl iodide generated from the decomposition of the promoter Me4NI under reaction conditions. The formation of acetyl iodide favors the cleaving efficiency of the inert unstrained C(sp3)―N bond of trimethylamine. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献
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Zachary S. Kean Dr. Sergey Akbulatov Dr. Yancong Tian Prof. Ross A. Widenhoefer Dr. Roman Boulatov Prof. Stephen L. Craig 《Angewandte Chemie (International ed. in English)》2014,53(52):14508-14511
A catalyst that couples a photoswitch to the biaryl backbone of a chiral bis(phosphine) ligand, thus allowing photochemical manipulation of ligand geometry without perturbing the electronic structure is reported. The changes in catalyst activity and selectivity upon switching can be attributed to intramolecular mechanical forces, thus laying the foundation for a new class of catalysts whose selectivity can be varied smoothly and in situ over a useful range by controlling molecular stress experienced by the catalyst during turnover. Forces on the order of 100 pN are generated, thus leading to measurable changes in the enantioselectivities of asymmetric Heck arylations and Trost allylic alkylations. The differential coupling between applied force and competing stereochemical pathways is quantified and found to be more efficient for the Heck arylations. 相似文献
186.
A series of imidazolium chlorides for the formation of tridentate CNO‐donor palladium(II) complexes featuring N‐heterocyclic carbene moieties have been developed from cheap and readily available starting materials with high yields. Their palladium complexes were prepared by reactions between the ligand precursors and PdCl2 using K2CO3 as base in pyridine with reasonable yields. These air‐stable metal complexes were characterized using 1H NMR and 13C{1H} NMR spectroscopy and elemental analyses. Heteronuclear multiple bond correlation experiments were performed to identify key NMR signals of these compounds. The structures of two of the complexes were also established by single‐crystal X‐ray diffraction analysis. One of these complexes was successfully applied in the direct C―H functionalization reactions between heterocyclic compounds and aryl bromides, producing excellent yields of coupled products. The coupling reactions were scalable, allowing grams of coupled products to be obtained with a mere 2 mol% of Pd loading. The catalyst system developed allowed the large‐scale preparation of several push–pull chromophores straightforwardly. Photophysical properties based on UV–visible and fluorescence spectroscopy for these chromophores were investigated. Deep blue photoluminescence with moderate quantum efficiency and twisted intramolecular charge transfer excited state were observed for these chromophores. Density functional theory (DFT) and time‐dependent DFT calculations were performed to support the experimental results. 相似文献
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In this paper, we develop a new mixed Mann iteration process to approximate the fixed points of mixed increasing operators in ordered Banach spaces and discuss the convergence analysis of the iterative sequences generated by the iteration process. As an application, we develop a new iterative method for solving a class of nonlinear integral equations. 相似文献
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In this paper, we consider the inviscid 3D Boussinesq system in Besov spaces and obtain the lower bound for the lifespan of solutions. 相似文献
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