The Development of Bulky Palladium NHC Complexes for the Most‐Challenging Cross‐Coupling Reactions

Palladium-catalyzed cross-coupling reactions enable organic chemists to form CC bonds in targeted positions and under mild conditions. Although phosphine ligands have been intensively researched, in the search for even better cross-coupling catalysts attention has recently turned to the use of N-heterocyclic carbene (NHC) ligands, which form a strong bond to the palladium center. PEPPSI (pyridine-enhanced precatalyst preparation, stabilization, and initiation) palladium precatalysts with bulky NHC ligands have established themselves as successful alternatives to palladium phosphine complexes. This Review shows the success of these species in Suzuki–Miyaura, Negishi, and Stille–Migita cross-couplings as well as in amination and sulfination reactions.