Catalytic Reactions Involving the Oxidative Addition of Si─Halogen and Si─Pseudohalogen Bonds as a Key Step

The oxidative addition of C-halogen bonds of aryl halides or alkyl halides is a critical step in a wide variety of transition-metal-catalyzed C─C and C-heteroatom bond formation reactions. In contrast, the oxidative addition of Si-halogen bonds of halosilanes has not been used in the development of transition metal-catalyzed reactions, although halosilanes are known to be highly reactive in many organic reactions with oxygen-containing compounds. However, recent progress in transition metal-catalyzed reactions using halosilanes has resulted in several synthetically useful and revolutionary methodologies concerning organosilicon synthesis through the oxidative addition of Si-halogen bonds, even less reactive Si─Cl bonds. This review will focus on transition metal-catalyzed reactions of C─C multiple bonds, such as alkenes, alkynes, and 1,3-dienes with R3Si-X (I, Br, Cl, and OTf), in which the oxidative addition of a Si─X bond appears to be a key step. In addition, the transition metal-catalyzed cross-coupling, cross-electrophile coupling, and three-component cross-electrophile coupling reactions with R3Si-X (I, Br, Cl, F, and OTf) are also discussed.