Fluorine is the most electronegative element in the periodic table. Thus, activation of the carbon–fluorine (C−F) bond, the strongest single bond to carbon, has attracted considerable interest from both experimentalists and theoreticians. In comparison with numerous approaches to activate C−F bonds, the aromaticity‐promoted method is less developed. Herein, we demonstrate that the C−F bond activation could be achieved by a facile tautomerization, benefitting from aromaticity, which can stabilize both the transition states and products. Our findings highlight an important application of aromaticity in the C−F bond activation, providing experimentalists with an alternative approach to activate C−F bonds.

https://onlinelibrary.wiley.com/doi/abs/10.1002/asia.201900294