Total Synthesis of Rhazinilam through Gold-Catalyzed Cycloisomerization–Sulfonyl Migration and Palladium-Catalyzed Suzuki–Miyaura Coupling of Pyrrolyl Sulfonates

We report the first general conditions for the challenging Suzuki–Miyaura reaction with pyrrole-related sulfonate coupling partners (24 examples, 60–97%). Bis­(dichloro)­bis­(2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl)­palladium­(II) precatalyst ensures the high efficiency of the reaction. The total synthesis of rhazinilam, a monoterpenoid indole alkaloid, highlights such cross-coupling as well as the simple preparation of pyrrolyl sulfonates by N-to-O 1,5-sulfonyl migration catalyzed by gold­(I) (15 examples, 54–93%).