Aggregation‐enabled alkene insertion into carbon–halogen bonds
Meng‐Yao Li,
Xiao‐Mei Nong,
Han Xiao,
Ao Gu,
Shuyang Zhai,
Jiatong Li,
Ge Zhang,
Ze‐Jian Xue,
Yingbin Liu,
Chunsen Li,
Guo‐Qiang Lin,
Chen‐Guo Feng
Affiliations
Meng‐Yao Li
Shanghai Cancer Institute Department of Biliary‐Pancreatic Surgery Renji Hospital Affiliated to Shanghai Jiao Tong University School of Medicine Shanghai China
Xiao‐Mei Nong
Shanghai Cancer Institute Department of Biliary‐Pancreatic Surgery Renji Hospital Affiliated to Shanghai Jiao Tong University School of Medicine Shanghai China
Han Xiao
State Key Laboratory of Structural Chemistry Fujian Institute of Research on the Structure of Matter Chinese Academy of Sciences Fuzhou China
Ao Gu
Shanghai Cancer Institute Department of Biliary‐Pancreatic Surgery Renji Hospital Affiliated to Shanghai Jiao Tong University School of Medicine Shanghai China
Shuyang Zhai
Shanghai Cancer Institute Department of Biliary‐Pancreatic Surgery Renji Hospital Affiliated to Shanghai Jiao Tong University School of Medicine Shanghai China
Jiatong Li
Shanghai Cancer Institute Department of Biliary‐Pancreatic Surgery Renji Hospital Affiliated to Shanghai Jiao Tong University School of Medicine Shanghai China
Ge Zhang
Shanghai Institute of Organic Chemistry Chinese Academy of Sciences Shanghai China
Ze‐Jian Xue
Shanghai Institute of Organic Chemistry Chinese Academy of Sciences Shanghai China
Yingbin Liu
Shanghai Cancer Institute Department of Biliary‐Pancreatic Surgery Renji Hospital Affiliated to Shanghai Jiao Tong University School of Medicine Shanghai China
Chunsen Li
State Key Laboratory of Structural Chemistry Fujian Institute of Research on the Structure of Matter Chinese Academy of Sciences Fuzhou China
Guo‐Qiang Lin
The Research Center of Chiral Drugs Innovation Research Institute of Traditional Chinese Medicine Shanghai Frontiers Science Center for Traditional Chinese Medicine Chemical Biology Shanghai University of Traditional Chinese Medicine Shanghai China
Chen‐Guo Feng
The Research Center of Chiral Drugs Innovation Research Institute of Traditional Chinese Medicine Shanghai Frontiers Science Center for Traditional Chinese Medicine Chemical Biology Shanghai University of Traditional Chinese Medicine Shanghai China
Abstract Molecular aggregation affects the electronic interactions between molecules and has emerged as a powerful tool in material science. Aggregate effect finds wide applications in the research of new physical phenomena; however, its value for chemical reaction development has been far less explored. Herein, we report the development of aggregation‐enabled alkene insertion into carbon–halogen bonds. The spontaneous cleavage of C–X (X = Cl, Br, or I) bonds generates an intimate ion pair, which can be quickly captured by alkenes in an aggregated state. Additional catalysts or promoters are not necessary under such circumstances, and solvent quenching experiments indicate that the aggregated state is critical for achieving such sequences. The ionic insertion mode is supported by mechanistic studies, density functional theory calculations, and symmetry‐adapted perturbation theory analysis. Results also show that the non‐aggregated state may quench the transition state and terminate the insertion process.
