Enantioselective α‐Allylation of Acyclic Esters Using B(pin)‐Substituted Electrophiles: Independent Regulation of Stereocontrol Elements through Cooperative Pd/Lewis Base Catalysis

Cooperation between a Lewis base and Pd catalyst enables the direct enantioselective α-functionalization of aryl and vinyl acetic acid esters using a bifunctional B(pin)-substituted electrophile. Critical to the success of this method was the recognition that both catalysts could control the necessary stereochemical aspects; the Lewis base catalyst controls the enantioselectivity of the reaction, whereas the Pd catalyst regulates alkenyl-B(pin) configuration. This is the first example of using cooperative catalysis to control both stereochemical features during Pd-catalyzed allylic alkylation.