This review highlights the transition metal-catalyzed reactions in which the oxidative addition of R₃Si-X (I, Br, Cl, F, and OTf) appears to be a key step. The reaction of C─C multiple bonds, such as alkenes, alkynes, and 1,3-dienes with R₃Si-X proceeds though silylmetalation. In addition, cross-coupling reactions, cross-electrophile coupling, and three-component cross-electrophile coupling reactions are also involved.

Abstract

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.