Lu Shuo, Zheng Tianyu, Ma Jiawei, Deng Zhangming, Qin Shengmeng, Chen Yu, Liang Yong
State Key Laboratory of Coordination Chemistry, Jiangsu Key Laboratory of Advanced Organic Materials, Chemistry and Biomedicine Innovation Center, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210023, China.
Angew Chem Int Ed Engl. 2022 May 16;61(21):e202201285. doi: 10.1002/anie.202201285. Epub 2022 Mar 21.
Aromatic ammonium and phosphonium salts are important synthetic intermediates and multifunctional materials, but para-selective functionalization of the aromatic salts remains a challenge. Here we develop an ionic ligand based on our newly designed "biphenyl-phenanthroline" skeleton and realize the Ir-catalyzed para-selective C-H borylation of seven types of aromatic quaternary ammonium and phosphonium salts. Gram-scale transformation, late-stage elaboration for drug molecule, and diversification of borylated products demonstrate the potential utility of this reaction. The mechanistic studies and computational analysis elucidate the origin of para-selectivity.
芳香铵盐和鏻盐是重要的合成中间体和多功能材料，但芳香盐的对位选择性官能团化仍然是一个挑战。在此，我们基于新设计的“联苯-菲咯啉”骨架开发了一种离子配体，并实现了铱催化的七种芳香季铵盐和鏻盐的对位选择性C-H硼化反应。克级规模的转化、药物分子的后期修饰以及硼化产物的多样化展示了该反应的潜在应用价值。机理研究和计算分析阐明了对位选择性的起源。
