Selectivity in Palladium-Catalyzed Allylic Substitution

The present chapter introduces the basic fundaments of the palladium-catalyzed allylic substitution reaction. After a brief introduction, the reaction is explored into the different steps of the catalytic cycle in a chronological order. Formation of the crucial eta(3)-allyl palladium complexes is first commented, followed by a brief description of the static isomerism and dynamic features related to these compounds. Synthetic opportunities to intercept these complexes are then presented. Selectivity is then addressed with a first focus on regioselectivity and memory effects. Finally, selected examples of enantioselective versions are presented and classified according to the position of the enantiodiscriminating step in the catalytic cycle.