JOURNAL OF ORGANIC CHEMISTRY
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2023
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IF 3.6
Benqiang Cui,Ye Tian,Yongchao Gao,Shaoyi Hua,Yanhui Shi,Changsheng Cao
Direct introduction of silyl radicals to forge C–Si bonds is of central importance in organic synthesis, owing to the formidable potential of silyl groups as coupling partners for further derivatization reactions to achieve more valuable compounds. Cleavage of heteroaromatic endocyclic carbon–heteroatom bonds to assemble C–Si bonds is scarce. Here, we demonstrate a dearomatization silylation of benzofurans and furopyridines via silyl radical addition and C(2)–O bond scission under metal-catalyst-free and mild conditions. Preliminary mechanistic experiments suggest that these transformations involve radical/single-electron transfer and [1,5]-Brook rearrangement processes. This protocol for the total synthesis of Doxepin and oxyresveratrol derivatives is carried out. The silylated products in several transformation reactions have proven to be useful as synthetic intermediates.
研究领域:
有机化学
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药物化学
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DOI
PubMed
高影响因子
JOURNAL OF ORGANIC CHEMISTRY
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2022
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IF 4.198
Yi-Fan Wang,Yu-Han He,Yan Su,Yang Ji,Rui Li
A palladium complex coordinated with a chiral SIPHOS ligand was evaluated as an efficient catalyst for asymmetric hydrosilylation of β-silyl styrenes with trichlorosilane and 23 1,2-bis(silyl) chiral compounds were produced. Good to excellent enantioselectivities were observed with 1-aryl-2-silyl ethanols, where the trichlorosilyl groups of the hydrosilylation products were selectively converted into a hydroxyl group in the presence of pre-installed trialkylsilyl groups. Asymmetric hydrosilylation of β-silyl styrenes followed by methylation of the trichlorosilyl group gave stable 1,2-bis(silyl) chiral compounds 4 with excellent yields. DFT calculations of hydridopalladium B coordinated with a SIPHOS ligand, an intermediate of the hydrosilylation reaction, established the optical structures to be energy minima, and the structural information could well illustrate the enantioselectivity for the hydrosilylation reaction.
研究领域:
有机化学
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催化化学
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理论计算化学
✓ 已验证
DOI
高影响因子
Surfaces and Interfaces
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2024
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IF 5.7
Jun-Qing Ye,Pin-Xi Wang,Xin Rong,Qi-Da Ding,Jun-Feng Qian,Sheng-Chun Chen,Ming-Yang He,Qun Chen
Vinylsilane compounds are essential chemical feedstocks and intermediates in organic synthesis. A heterogeneous Cu-containing mesoporous ZSM-5 zeolite catalyst developed through an in-situ doping method can be used for preparing vinylsilane compounds via decarboxylative coupling with remarkable catalytic efficiency. The mesoporous structure along with the appropriate surface area and pore volume of the catalyst is likely to be responsible for facilitating mass transfer in the reaction process. Additionally, due to the suitable Brønsted and Lewis acid active sites, adsorption and activation of reactant molecules can be readily triggered to promote the generation of alkoxyl radicals, which is the crucial species to complete the catalytic cycle. Importantly, the transformation exhibits high efficiency, broad substrate scope, and good reusability for at least six cycles.
研究领域:
有机化学
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催化材料科学
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产品关联
DOI
高影响因子
Sustainable Chemistry and Pharmacy
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2023
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IF 6
Qingli Zhu,Xiao Chen,Heng Gu,Zhi Yun
With the rapid increasing of environmental pollution concerns and declining petroleum assets, bio-based lubricants industry has aroused increasingly more attention and study. The present paper proposed two methods (a two-step process and a direct hydrosiylation process) for the production of biolubricant from soybean oil with organosilicon. At first, soybean oil was subjected to transesterification with potassium hydroxide under certain conditions. Then, the transesterified soybean oil was undergone urea inclusion for obtaining unsaturated fatty acid methyl esters (UFAMEs). After urea inclusion, the content of UFAMEs was increased to 88.1%. Next, the chemical modification of UFAMEs by the two-step process (epoxidation and ring-opening reaction) and the direct hydrosiylation process (with triethylsilane in present of catalyst) were systematically studied, respectively. With the optimal conditions, the conversions of UFAMEs in the two-step process and direct hydrosiylation process were 86.1% and 82.1%, respectively. In addition, the structure characteristics of material and products were determined by Fourier-transformed infrared (FTIR) spectroscope and 29 Si-Nuclear magnetic resonance ( 29 Si-NMR) spectrascopy. The lubrication performances of the two products were proved to be much better than soybean oil according to industry standards. Therefore, both of the two processes appeared to be feasible for bio-lubricant production.
研究领域:
环境科学
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化学工程
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材料科学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
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2022
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IF 6.76
Feihong Ye,Liping Li,Jianyin Xu,Lu Zhou
Synthesization of 1H,1H,2H,2H-Perfluorooctyltrimethoxysilane through solvent-free hydrosilylation of 1H,1H,2H-perfluoro-1-octene with trimethoxysilane was efficiently conducted over the RuCl 3 ·3H 2 O catalyst. The synergistic action of Ru 3+ as the active center and the strong electronegativity of Cl − to attract the electron of the electron-donating group –OCH 3 in trimethoxysilane, activated the Si-H and thus promoted the reaction. The influences of different reaction conditions including feed order, feed ratio, catalyst dosage, reaction temperature and reaction time on the reaction yield were fully investigated, to conclude the optimized condition to achieve a yield of 86.80% was the feed of 1.2 mol trimethoxysilane per mole of 1H,1H,2H-perfluoro-1-octene, together with the addition of 9.56 × 10 −4 mol RuCl 3 ·3H 2 O per mole of trimethoxysilane, at 80 °C for 4 h; while the additive of CuCl to RuCl 3 ·3H 2 O catalyst could further improve the reaction yield at 50℃. Finally, after understanding the activity of Ru with different valence state, the reaction mechanism was also proposed.
研究领域:
化学工程
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材料科学
✓ 已验证
DOI
高影响因子
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