Palladium‐Catalyzed C−H Silylation through Palladacycles Generated from Aryl Halides

A highly efficient palladium‐catalyzed disilylation reaction of aryl halides through C−H activation has been developed for the first time. The reaction has broad substrate scope. A variety of aryl halides can be disilylated by three types of C−H activation, including C(sp2)−H, C(sp3)−H, and remote C−H activation. In particular, the reactions are also unusually efficient. The yields are essentially quantitative in many cases, even in the presence of less than 1 mol % catalyst and 1 equivalent of the silylating reagent under relatively mild conditions. The disilylated biphenyls can be converted into disiloxane‐bridged biphenyls. Choice of three: A palladium‐catalyzed disilylation reaction of aryl halides has been developed through C−H activation. The reaction has broad substrate scope and is unusually efficient. A variety of aryl halides can be disilylated by three types of C−H activation, including C(sp2)−H, C(sp3)−H, and remote C−H activation, in excellent yields. The method is scalable and features high atom economy.