Mixed Directing-Group Strategy: Oxidative C−H/C−H Bond Arylation of Unactivated Arenes by Cobalt Catalysis
Cong Du
College of Chemistry and Molecular Engineering, Zhengzhou University, Kexue avenue 100, Zhengzhou, P.R. China
These authors contributed equally to this work.
Search for more papers by this authorPeng-Xiang Li
College of Chemistry and Molecular Engineering, Zhengzhou University, Kexue avenue 100, Zhengzhou, P.R. China
These authors contributed equally to this work.
Search for more papers by this authorDr. Xinju Zhu
College of Chemistry and Molecular Engineering, Zhengzhou University, Kexue avenue 100, Zhengzhou, P.R. China
Search for more papers by this authorJian-Feng Suo
College of Chemistry and Molecular Engineering, Zhengzhou University, Kexue avenue 100, Zhengzhou, P.R. China
Search for more papers by this authorCorresponding Author
Dr. Jun-Long Niu
College of Chemistry and Molecular Engineering, Zhengzhou University, Kexue avenue 100, Zhengzhou, P.R. China
Search for more papers by this authorCorresponding Author
Prof. Mao-Ping Song
College of Chemistry and Molecular Engineering, Zhengzhou University, Kexue avenue 100, Zhengzhou, P.R. China
Search for more papers by this authorCong Du
College of Chemistry and Molecular Engineering, Zhengzhou University, Kexue avenue 100, Zhengzhou, P.R. China
These authors contributed equally to this work.
Search for more papers by this authorPeng-Xiang Li
College of Chemistry and Molecular Engineering, Zhengzhou University, Kexue avenue 100, Zhengzhou, P.R. China
These authors contributed equally to this work.
Search for more papers by this authorDr. Xinju Zhu
College of Chemistry and Molecular Engineering, Zhengzhou University, Kexue avenue 100, Zhengzhou, P.R. China
Search for more papers by this authorJian-Feng Suo
College of Chemistry and Molecular Engineering, Zhengzhou University, Kexue avenue 100, Zhengzhou, P.R. China
Search for more papers by this authorCorresponding Author
Dr. Jun-Long Niu
College of Chemistry and Molecular Engineering, Zhengzhou University, Kexue avenue 100, Zhengzhou, P.R. China
Search for more papers by this authorCorresponding Author
Prof. Mao-Ping Song
College of Chemistry and Molecular Engineering, Zhengzhou University, Kexue avenue 100, Zhengzhou, P.R. China
Search for more papers by this authorGraphical Abstract
[Co(acac)3]-catalyzed oxidative C−H/C−H bond arylation of unactivated arenes enables the transformation of a wide range of benzamides and arylpyridines to afford bifunctionalized biaryls. A single-electron transfer (SET) and a concerted metalation–deprotonation (CMD) are involved. Moreover, the aryl radicals were trapped by 2,6-di-tert-butyl-4-methylphenol to form benzylated products.
Abstract
A mixed directing-group strategy for inexpensive [Co(acac)3]-catalyzed oxidative C−H/C−H bond arylation of unactivated arenes has been disclosed. This strategy enables the arylation of a wide range of benzamide and arylpyridines effectively to afford novel bifunctionalized biaryls, which are difficult to achieve by common synthetic routes. Two different pathways, namely, a single-electron-transmetalation process (8-aminoquinoline-directed) and a concerted metalation–deprotonation process (pyridine-directed), were involved to activate two different inert aromatic C−H bonds. Moreover, the aryl radicals have been trapped by 2,6-di-tert-butyl-4-methylphenol to form benzylated products. This unique strategy should be useful in the design of other arene C−H/C−H cross-couplings as well.
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