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71.
Tong Zhang Nai-Xing Wang Yue-Hua Wu Zhan Yan Yalan Xing Jia-Long Wen Xue-Wang Gao 《Tetrahedron letters》2018,59(51):4525-4527
A novel direct alkylation of thiophenes via bis-coupling with vinyl acetates has been developed. To the best of our knowledge, this represents the first report of the iron-catalysed coupling of two thiophenes with vinyl groups. Utilizing earth-abundant, inexpensive, and non-toxic iron catalysts, this methodology converts simple thiophenes to symmetrical dithienylethane derivatives under mild conditions in one step. 相似文献
72.
Zhen-Yu Wang Jia-Hao Wan Gao-Yin Wang Rui Wang Ruo-Xing Jin Quan Lan Xi-Sheng Wang 《Tetrahedron letters》2018,59(23):2302-2305
An efficient nickel-catalyzed reductive relay cross-coupling of internal alkenes with alkyl (or aryl) halides has been developed. This method has demonstrated broad substrate scope, mild reaction conditions and excellent terminal-selectivity. Moreover, this efficient strategy could be applied to the terminal-selective alkylation of isomeric mixtures of internal alkenes. 相似文献
73.
Jian Chen Lifu Wu Yue Zhao Prof. Shaolin Zhu 《Angewandte Chemie (International ed. in English)》2023,62(44):e202311094
Catalytic methods which control multiple stereogenic centers simultaneously are highly desirable in modern organic synthesis and chemical manufacturing. Herein, we report a regio-, enantio-, and diastereoselective NiH-catalyzed hydroalkylation process which proceeds with simultaneous control of vicinal stereocenters originating from two readily accessible partners, prochiral internal alkenes (enamides or enecarbamates) and racemic alkyl electrophiles (α-bromoamides or Katritzky salts). This reaction produces high-value β-aminoamides and their derivatives under mild conditions and with precise selectivity. Preliminary studies of the mechanism indicate that the reaction involves an enantioselective syn-hydronickelation to generate an enantiomerically enriched alkylnickel(II) species. Subsequent enantioconvergent alkylation with a racemic alkyl electrophile generates the desired product as a single stereoisomer. 相似文献
74.
Naoki Tsuchiya Tetsuhiro Yamamoto Hiroki Akagawa Prof. Dr. Takashi Nishikata 《Angewandte Chemie (International ed. in English)》2023,62(21):e202301343
Herein, we report a copper-catalyzed stereospecific fluorination involving CsF and α-bromocarboxamides as tertiary alkyl sources that, unlike traditional stereospecific routes involving stereoinversive SN2 reactions, proceeds with retention of stereochemistry. The developed stereospecific Cu-catalyzed reaction is among the most efficient methods for synthesizing fluorinated molecules that possess highly congested stereogenic carbon centers. Mechanistic studies revealed that the combined reactivity of CuF2 and Cs salt is essential for completing the catalytic cycle. Our catalytic system underwent fluorination exclusively with tertiary alkyl bromides and did not react with primary alkyl bromides, indicating that this stereospecific fluorination methodology is suitable for synthesizing fluorinated building blocks possessing stereo-defined F-containing tertiary carbon stereogenic center. 相似文献
75.
Yun-Cheng Luo Ming-Kuan Wang Ling-Chao Yu Prof. Dr. Xingang Zhang 《Angewandte Chemie (International ed. in English)》2023,62(37):e202308690
The selective transition-metal catalyzed C−F bond functionalization of inexpensive industrial fluorochemicals represents one of the most attractive approaches to valuable fluorinated compounds. However, the selective C(sp2)−F bond carbofunctionalization of refrigerant hydrofluoroolefins (HFOs) remains challenging. Here, we report a nickel-catalyzed selective C(sp2)−F bond alkylation of HFO-1234yf with alkylzinc reagents. The resulting 2-trifluoromethylalkenes can serve as a versatile synthon for diversified transformations, including the anti-Markovnikov type hydroalkylation and the synthesis of bioactive molecule analogues. Mechanistic studies reveal that lithium salt is essential to promote the oxidative addition of Ni0(Ln) to the C−F bond; the less electron-rich N-based ligands, such as bipyridine and pyridine-oxazoline, feature comparable or even higher oxidative addition rates than the electron-rich phosphine ligands; the strong σ-donating phosphine ligands, such as PMe3, are detrimental to transmetallation, but the less electron-rich and bulky N-based ligands, such as pyridine-oxazoline, facilitate transmetallation and reductive elimination to form the final product. 相似文献
76.
Peng Zhu Jinshan Wang Fei Xia Wei Zhang Haiou Liu Prof. Xiongfu Zhang 《欧洲无机化学杂志》2023,26(9):e202200664
Sheet-like ZSM-5 has been regarded as a promising material for catalytic applications due to its diffusion superiority. However, it still remains a challenge to obtain a desirable sheet-like morphology because of the complex synthesis process of zeolites. Here, a facile strategy for synthesizing sheet-like ZSM-5 is developed by only adding ethanol as zeolite growth modifier in the synthesis gel. It is thought that ethanol might be preferentially absorbed on the {010} surface of zeolite crystals, interact with the exposed silicon hydroxyl groups on the crystal {010} facet, and suppress the growth of b axis, resulting in the sheet-like shape. Through finely tunning synthesis parameters, sheet-like ZSM-5 crystals with thin b-axis thickness of 90 nm and different aspect ratios could be obtained. Owing to its shorter diffusion path and optimized acidity, sheet-like ZSM-5 exhibits better catalytic performance than conventional ZSM-5 in the alkylation of benzene with ethanol. 相似文献
77.
Qing-yun Wu Long-long Ma Jin-xing Long Ri-yang Shu Qi Zhang Tie-jun Wang Ying Xu 《化学物理学报(中文版)》2016,29(4):474-480
E cient conversion of lignin to fine chemicals and biofuel become more and more attractive in biorefinery. In this work, we used a series of silica-alumina catalysts (i.e., SiO2-Al2O3, HY, Hβ, and HZSM-5) to degrade lignin into arenes and phenols. The relationship between the catalyst structure and lignin depolymerization performance was investigated. The results showed that both acidity and pore size of the catalyst could in uence the conversion of lignin. In the volatilizable product, phenols were identified as the main phenolic monomers via gas chromatography-mass spectrometer. SiO2-Al2O3 was the most effcient catalyst, giving 90.96% degree of conversion, 12.91% yield of phenols, and 2.41% yield of arenes in ethanol at 280℃ for 4 h. The Fourier transform infrared spectroscopy and 1H nuclear magnetic resonance spectroscopy analysis demonstrated that deoxygenation and alkylation occurred in this process. The effect of solvents was also investigated and the results showed that ethanol was the most effcient solvent. 相似文献
78.
79.
由异丁烷和1-丁烯烷基化合成高辛烷值汽油虽已被广泛用于工业生产,但由于液体酸催化剂存在许多缺点,寻找固体酸催化剂——分子筛、磺酸树脂及固体超强酸已受到国内外学者的广泛重视。对超强酸的研究多集中在SO_4~(2-)/氧化物催化剂上,此类催化剂的酸强度高、热稳定性好、制备简单,对异丁烷、1-丁烯烷基化具有较高的反应活性,但存在着积炭、寿命 相似文献
80.
Simon J. Coles Michael B. Hursthouse David G. Kelly Andrew J. Toner Neil M. Walker 《Journal of organometallic chemistry》1999,580(2):11367
[TiCl2(salen)] (1) reacts with AlMe3 (1:2) to give the heterometallic Ti(III) and Ti(IV) complexes [Ti{(μ-Cl)(AlMe2)}{(μ-Cl)(AlMe2X)}(salen)] (X=Me or Cl) (2) and [TiMe{(μ-Cl)(AlCl2Me)}(salen)] (3). Addition of diethyl ether to 3 affords [Ti(Me)Cl(salen)] (4). The analogous reaction of [TiBr2(salen)] (5) gives the crystallographically characterised [Ti{(μ-Br)(AlMe2)}{(μ-Br)(AlMe2X)}(salen)] (X=Me or Br) (6) and [Ti(Me)Br(salen)] (7) in a single step, whilst the comparable reaction of [TiCl2{(3-MeO)2salen}] (8) with AlMe3 yields [Ti(Me)Cl{(3-MeO)2salen}] (9) with no evidence of titanium(III) species. Reactivity of both halide and methyl groups of 4 has been probed using magnesium reduction, SbCl5 and AgBF4 halide abstraction and SO2 insertion reactions. Hydrolysis of [Ti(Me)X(L)] complexes affords μ-oxo species [TiX(L)]2(μ-O) [X=Cl, L=salen (13); X=Br, L=salen (14); X=Cl, L=(3-MeO)2salen (15)]. 相似文献