Palladium-catalyzed remote allylation of styrene derivatives: DFT calculations unraveling regioselectivity controlled by non-covalent interactions

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Density functional theory calculations were employed to elucidate the mechanism and regioselectivity of palladium-catalyzed ligand-controlled remote allylation reactions in styrene derivatives. The reaction unfolds sequentially through S N 2-type oxidative addition, β-H elimination, tandem metal walking, hydrofunctionalization and allylic substitution. The rate-determining step of the reaction is identified as allylic substitution while the regioselectivity is influenced by the hydrofunctionalization process. The calculated results provide a rationalization for experimental observations: the Cy-dppp ligand exclusively favors the 4,3-hydrofunctionalization product, whereas the 3,4,5-(OMe) 3 Ph-dppp ligand selectively yields the 1,4-hydrofunctionalization product. The distinctive regioselectivity stemming from these two ligands is primarily governed by unique and pivotal non-covalent interactions between the ligand and the substrate.