文献类型：期刊文献

英文题名：Switchable Phenanthroline-Cu Catalysts for Enantioselective Alkynylation and Amination of Cyclic Diaryliodonium Salts

作者：Liu, Yanfei[1,2];Ma, Yuzhen[1,2];Liu, Pei-Zhi[3,4,5];Shen, Chen[1,2];Cen, Shouyi[1,2];Zhu, Yuan-Yuan[6,7];Peng, Qian[3,4,5];Zhang, Zhipeng[1,2]

机构：[1]East China Univ Sci & Technol, Sch Chem & Mol Engn, Feringa Nobel Prize Scientist Joint Res Ctr, Key Lab Adv Mat,Frontiers Sci Ctr Materiobiol & Dy, Shanghai 200237, Peoples R China;[2]East China Univ Sci & Technol, Feringa Nobel Prize Scientist Joint Res Ctr, Frontiers Sci Ctr Materiobiol & Dynam Chem, Sch Chem & Mol Engn,Joint Int Res Lab Precis Chem, Shanghai 200237, Peoples R China;[3]Nankai Univ, State Key Lab Elementoorgan Chem, Frontiers Sci Ctr New Organ Matter, Coll Chem, Tianjin 300071, Peoples R China;[4]Nankai Univ, Coll Chem, Tianjin Key Lab Biosensing & Mol Recognit, Tianjin 300071, Peoples R China;[5]Haihe Lab Sustainable Chem Transformat, Tianjin 300192, Peoples R China;[6]Hefei Univ Technol, Sch Chem & Chem Engn, Anhui Prov Key Lab Value Added Catalyt Convers & R, 193 Tunxi Rd, Hefei 230009, Peoples R China;[7]Hefei Univ Technol, Anhui Prov Engn Res Ctr Flexible & Intelligent Mat, 193 Tunxi Rd, Hefei 230009, Peoples R China

年份：2026

卷号：65

期号：2

外文期刊名：ANGEWANDTE CHEMIE-INTERNATIONAL EDITION

收录：;EI(收录号：20254719521522);WOS:【SCI-EXPANDED(收录号:WOS:001615605300001)】；

基金：The authors thank the Research Center of Analysis and Test, East China University of Science and Technology, for their help with the characterization. They acknowledge the National Natural Science Foundation of China (22371072, 92156017, 22571169), the Natural Science Foundation of Shanghai (24ZR1415000), the Natural Science Foundation of Tianjin (24JCZDJC00750), the Fundamental Research Funds for the Central Universities (222201717003, JKVJ1251010, SLJ13233303 and YJ0142225), the Science and Technology Commission of Shanghai Municipality (24DX1400200), the Haihe Laboratory of Sustainable Chemical Transformation of Tianjin (24HHWCSS00019), the Program of Introducing Talents of Discipline to Universities (B16017), the "Frontiers Science Center for New Organic Matter", Nankai University (63181206) and the Shanghai Postdoctoral Excellence Program (2022145) for their generous financial support.

语种：英文

外文关键词：Alkynylation; Amination; Copper; Enantioselectivity; Homogeneous catalysis

摘要：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.