Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Ling-Ling Road, Shanghai, 200032, China.
Syngenta, Jealott's Hill International Research Centre, Bracknell, Berkshire, RG42 6EY, UK.
Angew Chem Int Ed Engl. 2022 Jul 11;61(28):e202201240. doi: 10.1002/anie.202201240. Epub 2022 May 17.
A two-step strategy for the transition-metal-free C-H functionalization of arenes using unsymmetrical iodonium salts as versatile synthetic linchpins is presented. The key to the success of this strategy is the identification of the 3,5-dimethyl-4-isoxazolyl (DMIX) group as a superior dummy ligand, which enables not only site-selective C-H functionalization to afford unsymmetrical iodonium salts, but also highly selective aryl transfer during the subsequent metal-free coupling reaction. Both electron-rich and moderately electron-deficient arenes can be converted into the iodonium salts through C-H functionalization, allowing for diverse structural elaboration by metal-free C-N, C-C, C-S, and C-O coupling.
本文提出了一种使用不对称碘𬭩盐作为多功能合成桥联试剂的无过渡金属芳基 C-H 功能化的两步策略。该策略的关键是确定 3,5-二甲基-4-异恶唑基（DMIX）作为优越的虚拟配体，它不仅可以实现选择性 C-H 功能化以得到不对称碘𬭩盐，而且可以在随后的无金属偶联反应中实现高度选择性的芳基转移。富电子和中等缺电子芳基都可以通过 C-H 功能化转化为碘𬭩盐，通过无金属 C-N、C-C、C-S 和 C-O 偶联进行多样化的结构修饰。
