Copper‐Catalyzed Asymmetric 1,4‐Aryl/Alkynylation of 1,3‐Enynes to Access Axially Chiral Tetrasubstituted Allenes

• Published in: ChemCatChem 2023-08, Vol.15 (16), p.n/a
• Main Authors: Huang, Han, Zhang, Haiyan, Wang, Qiaoling, Sun, Youwen, Su, Lei, Xu, Wenru, Ma, Yi, Kong, Sheng, Zhang, Guozhu, Guo, Rui
• Format: Article
• Language: English
• Subjects: 1,3-Enynes; Alkynes; Allenes; Aromatic compounds; Asymmetric radical coupling; Asymmetry; Copper; Copper catalysis; Diaryl iodonium salts; Enantiomers
• ISSN: 1867-3880; 1867-3899
• DOI: 10.1002/cctc.202300697

The asymmetric 1,4‐difunctionalization of 1,3‐enynes represents a concise and highly efficient strategy for the preparation of chiral allenes. Herein, we developed a copper‐catalyzed three‐component asymmetric radical 1,4‐aryl/alkynylation of 1,3‐enynes by employing inexpensive, readily available, and highly reactive diaryliodonium salts as precursors to generate aryl radicals. The success of this reaction relied on the use of iminophenyl oxazolinylphenylamines (IPOPA) as chiral ligands. The reaction exhibited good compatibility with various alkynes, 1,3‐enynes, and diaryliodonium salts, providing an effective method for constructing highly enantioselective tetrasubstituted axially chiral allene compounds. By employing inexpensive, readily available, and highly reactive diaryliodonium salts as precursors to generate aryl radicals, we developed a copper‐catalyzed asymmetric radical 1,4‐aryl/alkynylation of 1,3‐enynes, providing an effective method for constructing highly enantioselective tetrasubstituted axially chiral allene compounds. The success of this reaction relied on the use of iminobenzimidazolinylanilines (IPOPA) as chiral ligands. The reaction exhibited good compatibility with various alkynes, 1,3‐enynes, and diaryliodonium salts.