Enantioselective alpha-Allylation of Activated Esters via Cooperative Catalysis: Combining C1-Ammonium Enolates with Silyl-Substituted pi-Allyl-Palladium Electrophile

The direct, asymmetric alpha-allylation of esters is a powerful transformation in asymmetric chemistry. Our group has developed a protocol that merges two complementary and independent catalytic cycles in a cooperative fashion to facilitate the direct, catalytic, enantioselective construction of alpha-allylated acyclic esters. Facial selectivity is induced by the catalytically generated stereodefined organocatalytic nucleophile, directing the approach of a pi-(allyl)metal electrophile with high regio- and enantiocontrol. This report outlines the efforts towards developing a methodology that utilizes gamma-silylated allylic esters to expand the scope of our reaction and understand the effects the silane has on the regio- and stereochemical outcome of the reaction.