Gold and Bismuth Trimetallic Synergistic Redox Catalysis for Non‐Directed C─H Arylation with Aryl Bismuth
Abstract
Abstract The influence of substituent effects plays an important role on the efficiency and regioselectivity toward C─H activation of non‐directed arenes. Here, an unprecedented trimetallic synergistic redox catalysis system has been developed to achieve a highly efficient and orthogonal C─H arylation of non‐directed arenes with aryl bismuth. Both electron‐rich and ‐deficient aryl bismuth can proceed C─H arylation readily, thus affording an elegant strategy for the synthesis of challenging electron‐rich and sterically hindered biaryls by means of gold catalysis. Mechanistic studies reveal that Bi(V) species generated in‐situ from Ar─Bi(III) and NFSI is not only an arylation reagent but also an oxidant to form a critical Au(II)─Au(II)─Bi intermediate (detected by HRMS). Interestingly, the binding Bi‐moiety can modulate the electronic and steric environment of gold center through cooperative interactions, thus promoting the intramolecular transmetallation and reductive elimination. In addition, the synthetic robustness of this protocol has been demonstrated by gram‐scale experiments and late‐stage functionalization of complex molecules.
Article Details
Authors (11)
Duan‐Yang Liu
State Key Laboratory of Coordination Chemistry Jiangsu Key Laboratory of Advanced Organic Materials Chemistry and Biomedicine Innovation Center (ChemBIC) School of Chemistry and Chemical Engineering Nanjing University Nanjing 210023 China
Sitian Zhou
State Key Laboratory of Coordination Chemistry, Jiangsu Key Laboratory of Advanced Organic Materials, Chemistry and Biomedicine Innovation Center (ChemBIC), School of Chemistry and Chemical Engineering
Linhan Tian
State Key Laboratory of Coordination Chemistry Jiangsu Key Laboratory of Advanced Organic Materials Chemistry and Biomedicine Innovation Center (ChemBIC) School of Chemistry and Chemical Engineering Nanjing University Nanjing 210023 China
Honglei Zhang
Wei He
Kai Guo
State Key Laboratory of Southwestern Chinese Medicine Resources, and Innovative Institute of Chinese Medicine and Pharmacy
Congqing Zhu
State Key Laboratory of Coordination Chemistry, Jiangsu Key Laboratory of Advanced Organic Materials, School of Chemistry and Chemical Engineering
Chengjian Zhu
State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing Drum Tower Hospital, Jiangsu Key Laboratory of Advanced Organic Materials, Chemistry and Biomedicine Innovation Center (ChemBIC)
Sergey N. Konchenko
Nikolaev Institute of Inorganic Chemistry SB RAS Acad. Lavrentieva Ave. 3 Novosibirsk 630090 Russia
Weipeng Li
State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing Drum Tower Hospital, Jiangsu Key Laboratory of Advanced Organic Materials, Chemistry and Biomedicine Innovation Center (ChemBIC)
Jin Xie