<i>ortho</i> ‐C─H Alkylation of Aryl Chlorides by a Catellani Strategy
Abstract
Abstract Herein we report a general and practical palladium/norbornene catalysis system that effectively promotes difunctionalization of less reactive aryl chlorides. The key to success lies in the use of a particular norbornene (NBE) derivative as a powerful mediator that synergistically cooperates with the palladium catalyst and an electron‐rich phosphine ligand. A broad spectrum of electronically diverse aryl chlorides (57 examples) delivered the corresponding ortho ‐C─H alkylation/ ipso ‐olefination products in moderate to good yields. Notably, this protocol features excellent functional‐group tolerance, high concentration, scalability, and late‐stage functionalization of complex aryl chlorides. Furthermore, by integrating this chemistry with its counterparts involving aryl iodides and bromides, an intriguing triple‐Catellani reaction sequence was developed, rapidly increasing molecular complexity and diversity. Finally, DFT calculations were performed, revealing that noncovalent C─H⋯O interactions between the XPhos ligand and the NBE mediator promote the pivotal NBE insertion step.
Article Details
Authors (13)
Jian‐Shu Wang
Department of Laboratory Medicine Zhongnan Hospital of Wuhan University Engineering Research Center of Organosilicon Compounds & Materials (Ministry of Education) Hubei Key Lab on Organic and Polymeric OptoElectronic Materials College of Chemistry and Molecular Sciences The Institute for Advanced Studies and TaiKang Center for Life and Medical Sciences Wuhan University Wuhan 430072 China
Zequan Liu
Guangyin Qian
Department of Laboratory Medicine Zhongnan Hospital of Wuhan University Engineering Research Center of Organosilicon Compounds & Materials (Ministry of Education) Hubei Key Lab on Organic and Polymeric OptoElectronic Materials College of Chemistry and Molecular Sciences The Institute for Advanced Studies and TaiKang Center for Life and Medical Sciences Wuhan University Wuhan 430072 China
Xiahe Chen
Liming Cao
Tiaozhen Yu
Department of Laboratory Medicine Zhongnan Hospital of Wuhan University Engineering Research Center of Organosilicon Compounds & Materials (Ministry of Education) Hubei Key Lab on Organic and Polymeric OptoElectronic Materials College of Chemistry and Molecular Sciences The Institute for Advanced Studies and TaiKang Center for Life and Medical Sciences Wuhan University Wuhan 430072 China
Jinxiang Ye
State Key Laboratory of Metabolism and Regulation in Complex Organisms, Hubei Research Center of Fundamental Science-Chemistry, Engineering Research Center of Organosilicon Compounds and Materials (Ministry of Education), Hubei Key Lab on Organic and Polymeric OptoElectronic Materials, College of Chemistry and Molecular Sciences, the Institute for Advanced Studies, Taikang Center for Life and Medical Sciences, School of Artificial Intelligence
Yuanyuan Ma
Nurturing Center of Jiangsu Province for State Laboratory of AI Imaging & Interventional Radiology, Department of Radiology, Zhongda Hospital, School of Medicine
Shuqing Chen
Department of Epidemiology and Biostatistics, School of Public Health, Tongji Medical College, Huazhong University of Science and Technology
Zuo Yang
Department of Laboratory Medicine Zhongnan Hospital of Wuhan University Engineering Research Center of Organosilicon Compounds & Materials (Ministry of Education) Hubei Key Lab on Organic and Polymeric OptoElectronic Materials College of Chemistry and Molecular Sciences The Institute for Advanced Studies and TaiKang Center for Life and Medical Sciences Wuhan University Wuhan 430072 China
Hong‐Gang Cheng
Department of Laboratory Medicine Zhongnan Hospital of Wuhan University Engineering Research Center of Organosilicon Compounds & Materials (Ministry of Education) Hubei Key Lab on Organic and Polymeric OptoElectronic Materials College of Chemistry and Molecular Sciences The Institute for Advanced Studies and TaiKang Center for Life and Medical Sciences Wuhan University Wuhan 430072 China
Yun‐Fang Yang
Center for Phosphorescent Material Research State Key Laboratory of Green Chemical Synthesis and Conversion College of Chemical Engineering Zhejiang University of Technology Hangzhou Zhejiang 310014 P.R. China
Qianghui Zhou
State Key Laboratory of Metabolism and Regulation in Complex Organisms, Hubei Research Center of Fundamental Science-Chemistry, Engineering Research Center of Organosilicon Compounds and Materials (Ministry of Education), Hubei Key Lab on Organic and Polymeric OptoElectronic Materials, College of Chemistry and Molecular Sciences, the Institute for Advanced Studies, Taikang Center for Life and Medical Sciences, School of Artificial Intelligence