一种使用高价碘进行C(sp)-H羟基化和酰胺化的统一光氧化还原催化策略。

Li Guo-Xing, Morales-Rivera Cristian A, Gao Fang, Wang Yaxin, He Gang, Liu Peng, Chen Gong

State Key Laboratory and Institute of Elemento-Organic Chemistry , College of Chemistry , Collaborative Innovation Center of Chemical Science and Engineering (Tianjin) , Nankai University , Tianjin 300071 , China . Email:

Department of Chemistry , University of Pittsburgh , Pittsburgh , PA 15260 , USA . Email:

Chem Sci. 2017 Oct 1;8(10):7180-7185. doi: 10.1039/c7sc02773g. Epub 2017 Sep 4.

We report a unified photoredox-catalysis strategy for both hydroxylation and amidation of tertiary and benzylic C-H bonds. Use of hydroxyl perfluorobenziodoxole (PFBl-OH) oxidant is critical for efficient tertiary C-H functionalization, likely due to the enhanced electrophilicity of the benziodoxole radical. Benzylic methylene C-H bonds can be hydroxylated or amidated using unmodified hydroxyl benziodoxole oxidant Bl-OH under similar conditions. An ionic mechanism involving nucleophilic trapping of a carbocation intermediate by HO or CHCN cosolvent is presented.

我们报道了一种用于叔碳和苄基碳氢键羟基化和酰胺化的统一光氧化还原催化策略。使用羟基全氟苯碘唑（PFBl-OH）氧化剂对于高效的叔碳碳氢键官能化至关重要，这可能是由于苯碘唑自由基的亲电性增强所致。在类似条件下，苄基亚甲基碳氢键可以使用未修饰的羟基苯碘唑氧化剂Bl-OH进行羟基化或酰胺化。本文提出了一种离子机制，涉及由HO或CHCN共溶剂对碳正离子中间体进行亲核捕获。