Pd-Catalyzed Suzuki-Miyaura and Hiyama-Denmark Couplings of Aryl Sulfamates.

Using a recently discovered precatalyst, the first Pd-catalyzed Suzuki-Miyaura reactions using aryl sulfamates that occur at room temperature are reported. In complementary work, it is demonstrated that a related precatalyst can facilitate the coupling of aryl silanolates, which are less toxic and reactive nucleophiles than boronic acids with aryl chlorides. By combining our results using modern electrophiles and nucleophiles, the first Hiyama-Denmark reactions using aryl sulfamates are reported.