Copper‐Catalyzed Regio‐ and Diastereoselective Dearomative Carbosilylation of Unactivated Arenes by Intercepting the Dienyl Radical
Abstract
Abstract The radical‐mediated dearomatization of aromatic systems to generate cyclohexadienyl radical intermediates represents a crucial strategy for constructing three‐dimensional molecular architectures. Conventional approaches typically through ipso ‐addition and subsequent proton/oxygen/carbon dioxide trapping to suppress rapid re‐aromatization, significantly constraining product diversity. Furthermore, dearomative bifunctionalization reactions—which offer enhanced step‐ and atom‐economy—remain substantially underdeveloped. Herein, we disclose a copper‐catalyzed radical dearomative 1,4‐ and 1,2‐carbosilylation strategy applicable to diverse unactivated (hetero)aromatic substrates to selectively construct spiro‐ or fused‐cyclic products. The resulting vinyl and allylic silanes serve as versatile synthetic handles for downstream transformations, enabling the rapid construction of sp 3 ‐rich polycyclic scaffolds that are highly valuable in drug discovery. Mechanistic and DFT studies indicate that the reaction commences with copper(I)‐silicon‐mediated halogen atom transfer of readily available aryl iodides to generate aryl radicals. These reactive species exhibit dual pathways: direct ipso ‐addition to aromatic rings or 1,5‐hydrogen atom transfer followed by alkyl radical‐mediated ortho ‐addition. Subsequent trapping of the resulting dienyl radicals by copper(II)‐silicon species yields complex polycyclic systems containing cyclohexadienylsilicon frameworks with excellent chemo‐, regio‐ and diastereoselectivity. This methodology not only establishes a novel paradigm for copper‐catalyzed radical dearomative bifunctionalization but also provides an efficient radical ipso‐ and ortho ‐addition platform for synthesizing architecturally intricate polycyclic compounds.
Article Details
Authors (13)
Jialian Zheng
CCNU-uOttawa Joint Research Centre, State Key Laboratory of Green Pesticide, Engineering Research Center of Photoenergy Utilization for Pollution Control and Carbon Reduction, Ministry of Education, International Joint Research Center for Intelligent Biosensing Technology and Health, College of Chemistry, Central China Normal University (CCNU), 152 Luoyu Road, Wuhan, Hubei 430079, P. R. China
Kuili Liang
State Key Laboratory of Green Pesticide, Engineering Research Center of Photoenergy Utilization for Pollution Control and Carbon Reduction, Ministry of Education, College of Chemistry, Central China Normal University (CCNU), 152 Luoyu Road, Wuhan, Hubei 430079, P. R. China
Zi‐Qing Li
State Key Laboratory of Green Pesticide Engineering Research Center of Photoenergy Utilization for Pollution Control and Carbon Reduction Ministry of Education College of Chemistry Central China Normal University (CCNU) 152 Luoyu Road Wuhan Hubei 430079 P.R. China
Zunsheng Chen
State Key Laboratory of Green Pesticide Engineering Research Center of Photoenergy Utilization for Pollution Control and Carbon Reduction Ministry of Education College of Chemistry Central China Normal University (CCNU) 152 Luoyu Road Wuhan Hubei 430079 P.R. China
Jianzhong Lu
CCNU-uOttawa Joint Research Centre, State Key Laboratory of Green Pesticide, Engineering Research Center of Photoenergy Utilization for Pollution Control and Carbon Reduction, Ministry of Education, International Joint Research Center for Intelligent Biosensing Technology and Health, College of Chemistry, Central China Normal University (CCNU), 152 Luoyu Road, Wuhan, Hubei 430079, P. R. China
He Zhang
Beibei Yi
State Key Laboratory of Green Pesticide Engineering Research Center of Photoenergy Utilization for Pollution Control and Carbon Reduction Ministry of Education College of Chemistry Central China Normal University (CCNU) 152 Luoyu Road Wuhan Hubei 430079 P.R. China
Quanzhe Li
CCNU-uOttawa Joint Research Centre, State Key Laboratory of Green Pesticide, Engineering Research Center of Photoenergy Utilization for Pollution Control and Carbon Reduction, Ministry of Education, International Joint Research Center for Intelligent Biosensing Technology and Health, College of Chemistry, Central China Normal University (CCNU), 152 Luoyu Road, Wuhan, Hubei 430079, P. R. China
Qiuling Yang
State Key Laboratory of Green Pesticide Engineering Research Center of Photoenergy Utilization for Pollution Control and Carbon Reduction Ministry of Education College of Chemistry Central China Normal University (CCNU) 152 Luoyu Road Wuhan Hubei 430079 P.R. China
Jinrong Li
Zhihan Zhang
Central China Normal University , , 152 Luoyu Road , , ,
Guozhu Zhang
State Key Laboratory of Green Pesticide, Engineering Research Center of Photoenergy Utilization for Pollution Control and Carbon Reduction, Ministry of Education, College of Chemistry, Central China Normal University (CCNU), 152 Luoyu Road, Wuhan, Hubei 430079, P. R. China
Rui Guo