Mechanistic aspects of C–C bond formation involving allylpalladium complexes: the role of computational studies

Computational studies have proven to be a useful tool for the study of mechanistic aspects of reactions involving allylpalladium complexes as intermediates. Previous work on the mechanisms of reactions involving such intermediates is discussed, as well as our contributions in this field. Thus, we report on the study of the mechanism of the insertion of alkenes into allylpalladium intermediates involved in the Oppolzer carbocyclization, the possible reaction pathways for the allylstannylation of alkynes, and the carbon-carbon reductive elimination from bis(allyl)palladium complexes. Structures for elusive intermediates, transition states, and even a novel mechanism for the reductive elimination in allyl-allyl cross-coupling reactions have been proposed.