Switchable Phenanthroline‐Cu Catalysts for Enantioselective Alkynylation and Amination of Cyclic Diaryliodonium Salts
Abstract
Abstract Regio‐ and enantioselective ring‐opening alkynylation and amination of cyclic diaryliodoniums have been achieved through the development of conformationally switchable axially chiral phenanthroline‐Cu catalysts. A range of axially chiral biaryls bearing either an alkynyl substituent or an amide/oxalamide group were synthesized in good to excellent yield (up to 99%), with excellent regio‐ (up to >99:1) and enantioselectivity (up to 99.5:0.5 enantiomeric ratio [er]). Mechanistic studies revealed that the ion‐pairing interaction between the deprotonated phenolic hydroxy group within the ligand and the cyclic diaryliodonium cation played a significant role in controlling the enantioselectivity of the alkynylation reaction. In contrast, the switched conformation of the chiral phenanthroline‐Cu catalyst was found to be crucial to the high enantioselectivity obtained in the amination reaction.
Article Details
Authors (8)
Yanfei Liu
Yuzhen Ma
Key Laboratory for Advanced Materials and Joint International Research Laboratory of Precision Chemistry and Molecular Engineering, Feringa Nobel Prize Scientist Joint Research Center, Frontiers Science Center for Materiobiology and Dynamic Chemistry, School of Chemistry and Molecular Engineering East China University of Science & Technology Shanghai 200237 China
Pei‐Zhi Liu
State Key Laboratory of Elemento‐Organic Chemistry, Frontiers Science Center for New Organic Matter and Tianjin Key Laboratory of Biosensing and Molecular Recognition, College of Chemistry Nankai University Tianjin 300071 China
Chen Shen
Department of Laboratory Medicine, Sichuan Medical Laboratory Clinical Medicine Research Center
Shouyi Cen
Key Laboratory for Advanced Materials and Joint International Research Laboratory of Precision Chemistry and Molecular Engineering, Feringa Nobel Prize Scientist Joint Research Center, Frontiers Science Center for Materiobiology and Dynamic Chemistry, School of Chemistry and Molecular Engineering
Yuan‐Yuan Zhu
School of Chemistry and Chemical Engineering, Anhui Province Key Laboratory of Value‐Added Catalytic Conversion and Reaction Engineering, and Anhui Province Engineering Research Center of Flexible and Intelligent Materials Hefei University of Technology 193 Tunxi Road Hefei 230009 China
Qian Peng
State Key Laboratory of Elemento-Organic Chemistry and Tianjin Key Laboratory of Biosensing and Molecular Recognition College of Chemistry, Nankai University, 94 Weijin Road, Tianjin 300071, China
Zhipeng Zhang
College of Materials Science and Engineering