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%).