Modular Approach to Silicon‐Bridged Biaryls: Palladium‐Catalyzed Intramolecular Coupling of 2‐(Arylsilyl)aryl Triflates

Bridge of Si: Intramolecular direct arylation of 2-(arylsilyl)aryl triflates is catalyzed smoothly by Pd(OAc)2/PCy3 in the presence of Et2NH in dimethylacetamide (DMA), giving rise to the corresponding silicon-bridged biaryls in good to excellent yields. The new approach has led to the synthesis of a silicon-bridged 2-phenylindole (see scheme) that exhibits blue photoluminescence in the solid state with extremely high quantum yields.