Palladium-Catalyzed Allylic Alkylations via Titanated Nucleophiles: A New Early-Late Heterobimetallic System

Ti(OCHMe2)4 promoted the Pd2(dba)3-catalyzed addn. of carbon acids on allylic acetates. E.g., in the presence of Ti(OCHMe2)4, Pd2(dba)3, and PPh3, reaction of di-Et malonate and (E)-PhCH:CHCH2OAc gave (E)-PhCH:CHCH2CH(CO2Et)2 (86% yield). The reaction may also be carried out in the presence of Pd2(dba)3, PPh3, and BSA/AcOK.