Catalytic C-H Trifluoromethoxylation of Arenes and Heteroarenes

被引:93
作者
Zheng, Weijia [1 ,2 ]
Morales-Rivera, Cristian A. [3 ]
Lee, Johnny W. [1 ,2 ]
Liu, Peng [3 ]
Ngai, Ming-Yu [1 ,2 ]
机构
[1] SUNY Stony Brook, Dept Chem, Stony Brook, NY 11794 USA
[2] SUNY Stony Brook, Inst Chem Biol & Drug Discovery, Stony Brook, NY 11794 USA
[3] Univ Pittsburgh, Dept Chem, Pittsburgh, PA 15260 USA
关键词
arenes; photocatalysis; radicals; trifluoromethoxylation; ALPHA-FLUORINATED ETHERS; PHOTOREDOX CATALYSIS; BOND-CLEAVAGE; TRIFLUOROMETHYLATION; GENERATION; AMINATION; RADICALS; ALKENES;
D O I
10.1002/anie.201800598
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The intermolecular C-H trifluoromethoxylation of arenes remains a long-standing and unsolved problem in organic synthesis. Herein, we report the first catalytic protocol employing a novel trifluoromethoxylating reagent and redox-active catalysts for the direct (hetero)aryl C-H trifluoromethoxylation. Our approach is operationally simple, proceeds at room temperature, uses easy-to-handle reagents, requires only 0.03mol% of redox-active catalysts, does not need specialized reaction apparatus, and tolerates a wide variety of functional groups and complex structures such as sugars and natural product derivatives. Importantly, both ground-state and photoexcited redox-active catalysts are effective. Detailed computational and experimental studies suggest a unique reaction pathway where photoexcitation of the trifluoromethoxylating reagent releases the OCF3 radical that is trapped by (hetero)arenes. The resulting cyclohexadienyl radicals are oxidized by redox-active catalysts and deprotonated to form the desired products of trifluoromethoxylation.
引用
收藏
页码:9645 / 9649
页数:5
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