|
|||||
|
|
Unlocking Migratory Insertion in Gold Redox Catalysis |
|
| Authors: | Wenliang Wang Meiling Ding Dr Chuan-Gang Zhao Shuai Chen Prof Dr Chengjian Zhu Dr Jie Han Dr Weipeng Li Prof Dr Jin Xie |
| Institution: | 1. 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;2. 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
Green Catalysis Center, and College of Chemistry, Zhengzhou University, Zhengzhou, Henan, 450001 China |
| Abstract: | Exploration of elementary reactions in organometallic catalysis is an important method with which to discover new reactions. In this article, we report a gold(I)-catalyzed iodo-alkynylation of benzyne involving the merging of challenging migratory insertion and an oxidative addition process in gold catalytic cycle. A wide range of structurally diverse alkynyl iodides are good coupling partners in this iodo-alkynylation transformation. Both aliphatic and aromatic alkynyl iodides can react with benzynes smoothly to afford highly functionalized 1,2-disubstituted aromatics in moderate to good yields. Its good functional group compatibility and late-stage application of complex molecules demonstrate its synthetic robustness. Studies of the mechanism reveals the feasibility of oxidative addition and the DFT calculations demonstrate the possible migratory insertion of benzyne into AuIII-carbon bonds in the AuI/AuIII redox catalytic cycle, representing an important step towards an elementary reaction in gold chemistry research. |
| Keywords: | Gold Homogeneous Catalysis Mechanistic Study Migratory Insertion Oxidative Addition |