1,3-Stereocontrol in Stereoconvergent Allenylic Alkylation Enabled by Palladium and Chiral Phase-Transfer Cooperative Catalysis

• Published in: Organic letters Vol. 27; no. 29; pp. 8045 - 8051
• Main Authors: Qi, Hongbo, Wu, Wenhua, Wu, Dan-Xing
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 25.07.2025
• ISSN: 1523-7060; 1523-7052; 1523-7052
• DOI: 10.1021/acs.orglett.5c02416

A stereoconvergent allenylic alkylation of allenyl acetates with oxindoles has been established by palladium and chiral phase-transfer cooperative catalysis, allowing for an efficient construction of 1,3-nonadjacent stereogenic elements featuring both central and axial chirality. The noncovalent interactions of PTC create a chiral environment for nucleophilic attack on η3-allylpalladium intermediates. Mechanistic investigations reveal that the Pd/PTC synergistic action and matched chirality are both critical for stereocontrol, while PTC primarily determines the stereoselectivity. Notably, this work represents the first successful implementation of Pd/chiral PTC dual catalysis for 1,3-nonadjacent stereocontrol, thereby enriching the synthetic toolbox for constructing challenging remote stereocenters.