Enantioselective α‐Benzylation of Acyclic Esters Using π‐Extended Electrophiles

Abstract

The first asymmetric cooperative Lewis base/palladium catalyzedbenzylic alkylation of acyclic esters is reported. This reaction proceeds via stereodefined C1-ammonium enolate nucleophiles.C ritical to its success was the identification of benzylic phosphate electrophiles,w hichw ere uniquely reactive.A lkylated products were obtained with very high levels of enantioselectivity,a nd this method has been applied towardt he synthesis of the thrombin inhibitor DX-9065a.