Palladium‐Catalyzed Regio‐, Diastereo‐, and Enantioselective 1,2‐Arylfluorination of Internal Enamides

• Published in: Angewandte Chemie International Edition Vol. 60; no. 5; pp. 2699 - 2703
• Main Authors: Xi, Yang, Wang, Chenchen, Zhang, Qian, Qu, Jingping, Chen, Yifeng
• Format: Journal Article
• Language: English
• Published: Germany Wiley Subscription Services, Inc 01-02-2021
• Edition: International ed. in English
• Subjects: arylfluorination; enamide; Enantiomers; Fluorides; intermolecular reaction; Palladium; vicinal stereocenters; enamide; palladium; vicinal stereocenters; arylfluorination; intermolecular reaction
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.202012882

We herein describe a palladium‐catalyzed three‐component coupling of internal enamides, arylboronic acids, and Selectfluor to access the chiral β‐fluoroaminated moiety with up to 99 % ee. The prefunctionalized oxazolidinone substituted alkene enables the expedient construction of two vicinal stereocenters with excellent regio‐, diastereo‐, and enantioselectivities. The synthetic application is exhibited by selective transformation of the product into various vicinal benzylic fluoride derivatives.
The palladium‐catalyzed intermolecular oxidative 1,2‐arylfluorination of internal enamides is reported. The removable oxazolidinone group enabled the highly regio‐, diastereo‐, and enantioselective formation of β‐fluoroamine derivatives containing vicinal stereocenters with broad substrate scope under mild conditions.