Recent Advances in Transition-Metal-Catalyzed Silylations of Arenes with Hydrosilanes: C–X Bond Cleavage or C–H Bond Activation Synchronized with Si–H Bond Activation

Arylsilanes are valuable organosilicon compounds and attract significant research interest due to their promising applications in organic synthesis. The development of aromatic C–Si cross-coupling reactions represents a major challenge in both organosilicon chemistry and organic synthesis. A number of investigations are focused on developing transition-metal-catalyzed Si–C coupling reactions due to the associated high atom economy and superior functional group compatibility. This review describes recent advances in transition-metal-catalyzed selective silylations of aryl C–H and C–X (X = halide) bonds with hydrosilanes. 1 Introduction 2 Silylation of Arenes with Hydrosilanes via Aryl C–H Bond Activation 2.1 Rhodium-Catalyzed Dehydrogenative Silylations 2.2 Iridium-Catalyzed Dehydrogenative Silylations 2.3 Ruthenium-Catalyzed Dehydrogenative Silylations 2.4 Platinum-Catalyzed Dehydrogenative Silylations 2.5 Other Transition-Metal-Catalyzed Dehydrogenative Silylations 3 Silylation of Arenes with Hydrosilanes via Aryl C–X Bond Cleavage 3.1 Palladium-Catalyzed Silylations of Aryl Halides 3.2 Rhodium-Catalyzed Silylations of Aryl Halides 3.3 Platinum-Catalyzed Silylations of Aryl Halides 4 Conclusion