Continuous‐Flow Photocatalysis for the Direct C‐H Trifluoromethylation of Heterocycles with an Organic Photoredox Catalyst

Photocatalysis for direct C−H trifluoromethylation represents an ideal way to synthesize trifluoromethyl‐containing chemical compounds, but the conventional batch processes are inefficient with limited light penetration and indispensably irradiated for a long while. Herein, we report a continuous‐flow protocol for photocatalytic direct C−H trifluoromethylation of heterocycles in the presence of an organic photoredox catalyst: 2,4,6‐tris(diphenylamino)‐3,5‐difluorobenzonitrile (3DPA2FBN). In this approach, benefiting from the merger of organic photoredox catalysis and continuous‐flow techniques, a variety of trifluoromethylated heterocycles were rapidly synthesized up to 85 % yield with 80 min residence time under metal‐ and oxidant‐free reaction conditions. A continuous‐flow photocatalytic direct C−H trifluoromethylation of heterocycles has been successfully developed, enabling the construction of diverse trifluoromethylated heterocycles efficiently and rapidly.