Computational Studies of Versatile Heterogeneous Palladium-Catalyzed Suzuki, Heck, and Sonogashira Coupling Reactions

This perspective focuses on the mechanistic insights and complexity, which are difficult to acquire from pure experimental techniques, of the computational studies of Pd-catalyzed Suzuki, Heck, and Sonogashira carbon–carbon bond-forming reactions. These reactions consist of three fundamental steps including oxidative addition (OA), transmetalation (TM), and reductive elimination (RE) for the generation of carbon–carbon bonds from the bond-forming reactions of aryl halides (R1X) and organometallic species (R2M). Computational studies of these coupling reactions allow us to understand specific reaction pathways in the analysis of OA (resolving the linkage between coordination number and selectivity in Suzuki reaction), TM (the function of the base in the Suzuki reaction and various mechanistic options in the Sonogashira reaction), and RE (way of efficient β-hydride elimination in the Heck reaction). In addition, the reaction pathways and complexities in the full catalytic cycle of each reaction along with the future perspective are also discussed.