- Copper-Catalyzed Direct C-H Alkylation of Polyfluoroarenes by Using Hydrocarbons as an Alkylating Source
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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.
- Xie, Weilong,Heo, Joon,Kim, Dongwook,Chang, Sukbok
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supporting information
p. 7487 - 7496
(2020/08/06)
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- A general method for copper-catalyzed arene cross-dimerization
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A general method for a highly regioselective copper-catalyzed cross-coupling of two aromatic compounds using iodine as an oxidant has been developed. The reactions involve an initial iodination of one arene followed by arylation of the most acidic C-H bon
- Do, Hien-Quang,Daugulis, Olafs
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supporting information; experimental part
p. 13577 - 13586
(2011/10/10)
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- Nickel, manganese, cobalt, and iron-catalyzed deprotonative arene dimerization
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"Chemical Equation Presented" A number of first-row transition metal salts catalyze deprotonative dimerization of acidic arenes. Under the atmosphere of oxygen, nickel, manganese, cobalt, and iron chlorides have been shown to dimerize five- and six-membered ring heterocycles as well as electron-poor arenes. Both tetramethylpiperidide and dicyclohexylamide bases can be employed; however, the former afford slightly higher yields.
- Truong, Thanh,Alvarado, Joseph,Tran, Ly Dieu,Daugulis, Olafs
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scheme or table
p. 1200 - 1203
(2010/06/13)
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- An aromatic glaser-hay reaction
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(Chemical Equation Presented) A general method for copper-catalyzed deprotonative dimerization of arenes by employing oxygen as the terminal oxidant has been developed. Electron-rich and electron-poor heterocycles as well as electron-poor arenes are react
- Do, Hien-Quang,Daugulis, Olafs
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supporting information; experimental part
p. 17052 - 17053
(2010/03/25)
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