Enantioselective Palladium‐Catalyzed α‐Arylation of Acyclic Esters

A Pd-catalyzed enantioselective α-arylation of α,α-disubstituted esters with aryl bromides is established for the first time by employing P-chiral monophosphorus ligand 3-Pent-BIDIME as a chiral ligand, leading to a series of enantioenriched α,α-diaryl esters possessing quaternary carbon stereocenters in moderate to good yields and high enantioselectivities. The method features a broad substrate scope, mild conditions, excellent functional group compatibility, and low Pd loadings (as low as 1 mol%). The synthetic power of this protocol is exemplified by the efficient preparation of a chiral α,α-diaryl substituted γ-lactone and asymmetric synthesis of (R)-amolanone. DFT calculation revealed an NaBr-bridged downstream transmetallation and the importance of noncovalent interaction in controlling the enantioselectivity.