Ligand-Exchange-Enabled Axially Chiral Recognition in Asymmetric Aminopalladation/Olefination of 2‑Alkynylanilides

Chiral recognition for the synthesis of axially chiral biaryl units is a fundamental and challenging topic in organic synthesis. Herein, we documented that an efficient O-ligand exchange between the catalyst and substrate enabled axial chiral recognition in asymmetric aminopalladation/olefination of...

Full description

Saved in:
Bibliographic Details
Published in:ACS catalysis 2024-03, Vol.14 (6), p.4053-4065
Main Authors: Wang, Gang, Zhang, Ni, Yan, Bing-Xia, Zhang, Zhe-Wen, Li, Shi-Wei, Luo, Gen, Ye, Zhi-Shi
Format: Article
Language:English
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary:Chiral recognition for the synthesis of axially chiral biaryl units is a fundamental and challenging topic in organic synthesis. Herein, we documented that an efficient O-ligand exchange between the catalyst and substrate enabled axial chiral recognition in asymmetric aminopalladation/olefination of 2-alkynylanilides and vinyl trifluoromethanesulfonates, providing the axially chiral 3-alkenylindoles with up to 97% ee and 98% yield. This protocol features mild conditions, broad functional group tolerance, scalability, and late-stage modification of bioactive molecules. Experimental and computational studies hinted that O-ligand exchange between the (R)-BIDIME/Pd complex and the alkoxy group of 2-alkynylanilides was crucial to the success of stereoselectivity control.
ISSN:2155-5435
2155-5435
DOI:10.1021/acscatal.3c06032