Iron‐Catalyzed Fluoroalkylation of Arylborates with Sulfone Reagents: Beyond the Limitation of Reduction Potential

The iron‐catalyzed alkyl–aryl coupling reaction between sulfones and arylboron compounds has remained a challenge. We report the first iron‐catalyzed radical difluoroalkylation of arylborates with N‐heteroaryl sulfones. The coordination between the iron catalyst and the nitrogen atom of N‐heteroaryl sulfones was identified to be important in overcoming the reduction potential limitation of sulfones in the intermolecular single‐electron‐transfer process, which enables both fluoroalkyl N‐heteroaryl sulfones (with relatively high reduction potentials) and nonfluorinated alkyl N‐heteroaryl sulfones (with low reduction potentials) to serve as powerful alkylation reagents.