Ligand-Controlled Regioselectivity in Palladium-Catalyzed Cross Coupling Reactions

摘要

The reversal of regioselectivity in a Pd-catalyzed cross-coupling reaction of an aryl chloro triflate with different ligands, established by Fu and co-workers, has been studied computationally. C−O insertion was found to be controlled by Pd-HOMO ArO−LUMO interaction, where C−Cl insertion is facilitated by the lower C−Cl TS distortion energy. The greater reactivities of monoligated Pd species are due primarily to the lack of distortion of the Pd species.