Enantioselective Palladium‐Catalyzed α‐Arylation of Acyclic Esters

Abstract 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.