An Efficient C−Si/C−H Cross‐Coupling Reaction Enabled by a Radical Pathway

Abstract The methods for the cross‐coupling of aryl(trialkyl)silanes are long‐standing challenges due to the extreme inertness of C−Si(R 3 ) bond, though the reaction is environmentally friendly and highly regioselective to synthesize biaryls. Herein, we report a copper‐catalyzed cross‐coupling of aryl(trialkyl)silanes and aryl via a radical mechanism. The reaction proceeds efficiently with aryl sulfonium salts as limiting reagents, exhibits broad substrate scope, and provides an important synthetic strategy to acquire biaryls, exemplified by unsymmetrical fluorescence probes and late‐stage functionalization of drugs. Of note, the experimental and theoretical mechanistic studies revealed a radical mechanism where the copper catalyst and CsF play critical roles on the radical generation and desilylation process.