114467-73-1Relevant articles and documents
Nickel-Catalyzed Aromatic Cross-Coupling Difluoromethylation of Grignard Reagents with Difluoroiodomethane
Motohashi, Hirotaka,Mikami, Koichi
, p. 5340 - 5343 (2018)
The nickel-catalyzed cross-coupling difluoromethylation of the Grignard reagents with difluoroiodomethane is shown to provide the corresponding aromatic difluoromethyl products in excellent to moderate yields. The difluoromethylation proceeds smoothly within 1 h at room temperature with 1.5 equiv of the Grignard reagents in the presence of Ni(cod)2/TMEDA (2.5-0.5 mol %). Mechanistic studies clarify that the oxidative addition of the Ni(0) catalyst to difluoroiodomethane provides the TMEDA-Ni(II)(CF2H)I complex. This intermediate is transformed to TMEDA-Ni(II)(CF2H)Ph via transmetalation with PhMgBr. The reductive elimination takes place to give the aromatic cross-coupling difluoromethylation product along with regeneration of the TMEDA-Ni(0) catalyst. Electron paramagnetic resonance (EPR) and radical clock analyses of the nickel-catalyzed reaction provide no EPR active Ni(I) and Ni(III) species at around g = 2 and only a trace amount of the cyclization product.
Synthesis of gem-difluorides from aldehydes using DFMBA
Furuya, Tsukasa,Fukuhara, Tsuyoshi,Hara, Shoji
, p. 721 - 725 (2005)
Synthesis of gem-difluorides from aldehydes was effectively achieved using DFMBA and Et3N-3HF under microwave irradiation or conventional thermal heating. Both aromatic and aliphatic aldehydes could be converted to the corresponding gem-difluor
Electrochemical-Promoted Nickel-Catalyzed Oxidative Fluoroalkylation of Aryl Iodides
Zou, Zhenlei,Li, Heyin,Huang, Mengjun,Zhang, Weigang,Zhi, Sanjun,Wang, Yi,Pan, Yi
supporting information, p. 8252 - 8256 (2021/11/01)
This work describes a general strategy for metal-catalyzed cross-coupling of fluoroalkyl radicals with aryl halides under electrochemical conditions. The contradiction between anodic oxidation of fluoroalkyl sulfinates and cathodic reduction of low-valent nickel catalysts can be well addressed by paired electrolysis, allowing for direct introduction of fluorinated functionalities into aromatic systems.
Preparation method of difluoromethyl aromatic hydrocarbon compound
-
Paragraph 0056-0061, (2020/09/09)
The invention discloses a preparation method of a difluoromethyl aromatic hydrocarbon compound, which comprises the following steps: (1) in a nitrogen atmosphere, sequentially adding an aryl mono-substituted malonic acid substrate, a silver catalyst, alkali and a selective fluorine reagent into a reaction tube, adding a solvent, and reacting at corresponding temperature for 11-13 hours, wherein the molar ratio of the aryl mono-substituted malonic acid substrate to the silver catalyst to the alkali to the selective fluorine reagent is 1: (0.1-1): (0.5-5): (4-10); and (2) carrying out quenchingreaction by using 3M hydrochloric acid, and sequentially carrying out extraction, organic phase combination, washing, drying, organic phase spin-drying and purification on the reaction product to obtain the difluoromethyl aromatic hydrocarbon compound. The preparation method disclosed by the invention is simple to operate, simple and cheap in raw materials, easy in preparation, mild in conditions,good in functional group compatibility and very practical.
Controllable catalytic difluorocarbene transfer enables access to diversified fluoroalkylated arenes
Fu, Xia-Ping,Xue, Xiao-Song,Zhang, Xue-Ying,Xiao, Yu-Lan,Zhang, Shu,Guo, Yin-Long,Leng, Xuebing,Houk, Kendall N.,Zhang, Xingang
, p. 948 - 956 (2019/11/05)
Difluorocarbene has important applications in pharmaceuticals, agrochemicals and materials, but all these applications proceed using just a few types of reaction by taking advantage of its intrinsic electrophilicity. Here, we report a palladium-catalysed strategy that confers the formed palladium difluorocarbene (Pd=CF2) species with both nucleophilicity and electrophilicity by switching the valence state of the palladium centre (Pd(0) and Pd(ii), respectively). Controllable catalytic difluorocarbene transfer occurs between readily available arylboronic acids and the difluorocarbene precursor diethyl bromodifluoromethylphosphonate (BrCF2PO(OEt)2). From just this simple fluorine source, difluorocarbene transfer enables access to four types of product: difluoromethylated and tetrafluoroethylated arenes and their corresponding fluoroalkylated ketones. The transfer can also be applied to the modification of pharmaceuticals and agrochemicals as well as the one-pot diversified synthesis of fluorinated compounds. Mechanistic and computational studies consistently reveal that competition between nucleophilic and electrophilic palladium difluorocarbene ([Pd]=CF2) is the key factor controlling the catalytic difluorocarbene transfer.
