Regio- and Stereospecific <i>C</i>- and <i>O</i>-Allylation of Phenols via π-Allyl Pd Complexes Derived from Allylic Ester Carbonates

Two complementary strategies have been developed for the C- and O-allylation of phenols via a common π-allyl Pd complex. While O-allylation of phenols by this method is a well-recognized reaction of general utility, the associated para-selective C-allylation reaction is still in its infancy. Cationic π-allyl Pd intermediates, derived from allylic ester carbonates and palladium(0) catalyst, were found to undergo the Friedel-Crafts-type para-selective C-allylations with nine different phenols. Both C- and O-allylated products were obtained in good to excellent yields following a metal-catalyzed regio- and stereospecific substitutive 1,3-transposition. Conditions were also identified that control access to either allylated product. Finally, a study of the equilibrium established between the two allylation products revealed that the O-allylated compound was the kinetic product and the C-allylated compound the thermodynamic product.