Fenfen Xie,Fen Han,Yunying Yan,Haiqiong Li,Jianjun Hao,Linhai Jing,Pan Han
It is significant to develop novel difluoromethylation methods because of the important roles of difluoromethyl groups in the medicinal chemistry and material industries. Here, we developed a novel difluoromethylation–carboxylation and difluoromethylation–deuteration method triggered by a difluoromethyl radical generated by electroreduction of stable and easily available difluoromethyltriphenylphosphonium bromide. Various molecules containing difluoromethyl and carboxyl or deuterium groups can be synthesized through this method. The establishment of this method will provide an alternative to radical difluoromethylation reactions.
Yi Fang,Chunyi Liu,Jie Tang,Zheng Pei,Zhengping Chen
A photocatalytic synthesis of difluoromethylated selenides from selenosulfonates is described here. Bench-stable difluoromethyl phosphonium salt [Ph3PCF2H]Br reacts smoothly with selenosulfonates to give a series of functionalized difluoromethylated selenides in moderate to good yields via a radical process. This protocol is free of a stoichiometric base and reductant, has tolerance of functional groups, and has successful late-stage modification of bioactive molecules, which provides facile access to molecules of pharmaceutical relevance.
Huanhuan Song,Jingwen Li,Yinbin Zhang,Ke Chen,Le Liu,Junjie Zhang,Xin-Hua Duan,Mingyou Hu
Difluoromethylated heterocyclic compounds have found broad applications in numerous bioactive molecules. Herein, we report photoredox catalysis-induced direct C–H difluoromethylation of heterocycles by using bis(difluoromethyl) pentacoordinate phosphorane (PPh3(CF2H)2, 1) as the reagent. A variety of heterocycles, such as quinoxalin-2(1H)-one, thiophene, indole, and coumarin, are readily tailored with a difluoromethyl group. The method is featured as transition-metal-free by using an organic compound Erythrosin B as the catalyst and O2 as the oxidant.
Zhiwei Chen,Xiaoxiao Huang,Jie Sun,Yanmin Liu,Ziwei Li
Graphical A facile and effective metal-free decarboxylative cyclization of N -methacryloyl-2-phenylbenzimidazole with arylthio (oxy) difluoroacetic acids or α , α -aryldifluoroacetic acids was proposed to prepare a series of aryldifluoromethylated benzimidazole[2,1- a ] iso -quinoline-6(5 H )-one derivatives in medium to good yields with good functional group tolerance, readily available raw materials and simple operation. In addition, experimental studies showed that the CF 2 group of arylthiodifluoroacetic acids plays a crucial role in this conversion. A facile and effective metal-free decarboxylative cyclization of N -methacryloyl-2-phenylbenzimidazole with arylthio (oxy) difluoroacetic acids or α , α -aryldifluoroacetic acids was proposed to prepare a series of aryldifluoromethylated benzimidazole[2,1- a ] iso -quinoline-6(5 H )-one derivatives in medium to good yields with good functional group tolerance, readily available raw materials and simple operation. In addition, experimental studies showed that the CF 2 group of arylthiodifluoroacetic acids plays a crucial role in this conversion.
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