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