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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. [ABSTRACT FROM AUTHOR]

Abstract: Supported Pd nanoparticles catalyzed the reductive cycloisomerization of diynes to give 1,3‐dienes, and subsequent intermolecular [4+2] cycloaddition with dienophiles led to cyclohexene derivatives. Various diynes and dienophiles participated in the one‐pot reaction to give the corresponding products in good to high yields. Al2O3‐supported Pd catalysts were highly tolerant toward air and reusable. [ABSTRACT FROM AUTHOR]