Anionic Bisoxazoline Ligands Enable Copper‐Catalyzed Asymmetric Radical Azidation of Acrylamides. Issue 13 (17th February 2021)

• Record Type: Journal Article
• Authors: Wu, Lianqian; Zhang, Zhihan; Wu, Dunqi; Wang, Fei; Chen, Pinhong; Lin, Zhenyang; Liu, Guosheng
• Is Part Of: Angewandte Chemie international edition. Volume 60:Issue 13(2021)
• Page Start: 6997
• Page End: 7001
• Publication Date: 2021-02-17
• Subjects: acrylamides -- anionic bisoxazoline -- asymmetric azidation -- copper catalysis -- radical reactions; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.202015083
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: Asymmetric radical azidation for the synthesis of chiral alkylazides remains a tremendous challenge in organic synthesis. We report here an unprecedented highly enantioselective radical azidation of acrylamides catalyzed by 1 mol % of a copper catalyst. The substrates were converted to the corresponding alkylazides in high yield with good‐to‐excellent enantioselectivity. Notably, employing an anionic cyano‐bisoxazoline (CN‐Box) ligand is crucial to generate a monomeric Cu II azide species, rather than a dimeric Cu II azide intermediate, for this highly enantioselective radical azidation. Abstract : An unprecedented highly enantioselective radical azidation of acrylamides is reported, in which arrays of acrylamides can be converted to the corresponding alkylazides in high yield with good‐to‐excellent enantioselectivity. Notably, employing an anionic cyano‐bisoxazoline (CN‐Box) ligand is crucial for the generation of a monomeric Cu II azide species, rather than a dimeric Cu II azide intermediate.