1309657-06-4Relevant academic research and scientific papers
Copper-Catalyzed Direct C-H Alkylation of Polyfluoroarenes by Using Hydrocarbons as an Alkylating Source
Xie, Weilong,Heo, Joon,Kim, Dongwook,Chang, Sukbok
, p. 7487 - 7496 (2020)
Construction of carbon-carbon bonds is one of the most important tools in chemical synthesis. In the previously established cross-coupling reactions, prefunctionalized starting materials were usually employed in the form of aryl or alkyl (pseudo)halides or their metalated derivatives. However, the direct use of arenes and alkanes via a 2-fold oxidative C-H bond activation strategy to access chemoselective C(sp2)-C(sp3) cross-couplings is highly challenging due to the low reactivity of carbon-hydrogen (C-H) bonds and the difficulty in suppressing side reactions such as homocouplings. Herein, we present the new development of a copper-catalyzed cross-dehydrogenative coupling of polyfluoroarenes with alkanes under mild conditions. Relatively weak sp3 C-H bonds at the benzylic or allylic positions, and nonactivated hydrocarbons could be alkylated by the newly developed catalyst system. A moderate-to-high site selectivity was observed among various C-H bonds present in hydrocarbon reactants, including gaseous feedstocks and complex molecules. Mechanistic information was obtained by performing combined experimental and computational studies to reveal that the copper catalyst plays a dual role in activating both alkane sp3 C-H bonds and sp2 polyfluoroarene C-H bonds. It was also suggested that the noncovalent π-πinteraction and weak hydrogen bonds formed in situ between the optimal ligand and arene substrates are key to facilitating the current coupling reactions.
Copper(I)-Catalyzed Alkylation of Polyfluoroarenes through Direct C - H Bond Functionalization
Xu, Shuai,Wu, Guojiao,Ye, Fei,Wang, Xi,Li, Huan,Zhao, Xia,Zhang, Yan,Wang, Jianbo
, p. 4669 - 4672 (2015/04/14)
The copper(I)-catalyzed alkylation of electron-deficient polyfluoroarenes with N-tosylhydrazones and diazo compounds has been developed. This reaction uses readily available starting materials and is operationally simple, thus representing a practical method for the construction of C(sp2) - C(sp3) bonds with polyfluoroarenes through direct C - H bond functionalization. Mechanistically, copper(I) carbene formation and subsequent migratory insertion are proposed as the key steps in the reaction pathway.
Copper-catalyzed direct benzylation or allylation of 1,3-azoles with N -tosylhydrazones
Zhao, Xia,Wu, Guojiao,Zhang, Yan,Wang, Jianbo
, p. 3296 - 3299 (2011/04/24)
Cu-Catalyzed cross-coupling of N-tosylhydrazones with 1,3-azoles leads to the direct C-H benzylation or allylation. Cu carbene migratory insertion is proposed to play the key role in this transformation.
