Work

Enantioselective Palladium‐Catalyzed α‐Arylation of Acyclic Esters

Year: 2025

Type: article

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.

Source: Angewandte Chemie International Edition

DOI: 10.1002/anie.202505458

Authors: Jianxun Huang, Chao Pei, He Yang, Bin Wu, Wenjun Tang

Institutions: Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Novartis (China)

Language: English

Topic: Catalytic Cross-Coupling Reactions

Subfield: Organic Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: bronze

Funders: Novartis, National Natural Science Foundation of China, National Key Research and Development Program of China

Awards: G4941624838, G741154071