Heterogeneous gold‐catalyzed C(sp2)−H silylation is described. A variety of heteroarenes and electron‐rich arenes participated in gold‐catalyzed silylation to afford the corresponding heteroaryl and arylsilanes in good to excellent yields. A detailed mechanistic investigation corroborated that the cooperative catalysis of ether and O2‐activated gold nanoparticles realized heterolysis of the Si−H bond to generate silyl cations, which enabled subsequent electrophilic C−Si bond formation. The high activity, reusability and environmentally‐friendly nature of the heterogeneous gold catalysts as well as the scalability of the reaction system realize the sustainable synthesis of aryl and heteroarylsilanes.
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