Catalytic C−H Trifluoromethoxylation of Arenes and Heteroarenes |
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| Authors: | Weijia Zheng Cristian A Morales‐Rivera Johnny W Lee Peng Liu Prof Ming‐Yu Ngai |
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| Affiliation: | 1. Department of Chemistry, and Institute of Chemical Biology and Drug Discovery, Stony Brook University, Stony Brook, NY, USA;2. Department of Chemistry, University of Pittsburgh, Pittsburgh, PA, USA |
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| Abstract: | 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 0.03 mol % 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. |
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| Keywords: | arenes photocatalysis radicals trifluoromethoxylation |
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