Ming‐Shun Mei, Yanghui Zhang
Comprehensive Summary Fluoroalkoxylated heterocycles, such as indoles, holds significant importance in pharmaceuticals and biology. Herein, we report a copper‐mediated C4–H fluoroalkoxylation reaction of indoles via a transient directing group (TDG) strategy. This reaction exhibits excellent regioselectivity and broad functional group compatibility, offering a new approach for the synthesis of fluoroalkoxylated indoles. The reaction also represents an unprecedented example of 3d‐transition metal‐catalyzed C─H fluoroalkoxylation via a TDG strategy.