Nucleophilic Aryl Fluorination and Aryl Halide Exchange Mediated by a CuI/CuIII Catalytic Cycle

被引:220
作者
Casitas, Alicia [1 ]
Canta, Merce [1 ]
Sola, Miquel [1 ,2 ]
Costas, Miguel [1 ]
Ribas, Xavi [1 ]
机构
[1] Univ Girona, Dept Quim, QBIS Res Grp, E-17071 Girona, Catalonia, Spain
[2] Univ Girona, Inst Quim Computac, E-17071 Girona, Catalonia, Spain
基金
欧洲研究理事会;
关键词
F REDUCTIVE ELIMINATION; CARBON-HALOGEN BONDS; PALLADIUM FLUORIDE; COMPLEXES; LIGANDS; ACTIVATION; REACTIVITY; CONVERSION; CHEMISTRY; MECHANISM;
D O I
10.1021/ja2058567
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Copper-catalyzed halide exchange reactions under very mild reaction conditions are described for the first time using a family of model aryl halide substrates. All combinations of halide exchange (I, Br, Cl, F) are observed using catalytic amounts of Cu-I. Strikingly, quantitative fluorination of aryl X substrates is also achieved catalytically at room temperature, using common F- sources, via the intermediacy of aryl-Cu-III-X species. Experimental and computational data support a redox Cu-I/Cu-III catalytic cycle involving aryl X oxidative addition at the Cu-I center, followed by halide exchange and reductive elimination steps. Additionally, defluorination of the aryl-F model system can be also achieved with Cu-I at room temperature operating under a Cu-I/Cu-III redox pair.
引用
收藏
页码:19386 / 19392
页数:7
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