Zhang Wei, Chen Jia, Lin Jin-Hong, Xiao Ji-Chang, Gu Yu-Cheng
Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, China.
Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, China.
iScience. 2018 Jul 27;5:110-117. doi: 10.1016/j.isci.2018.07.004. Epub 2018 Jul 11.
The CFO functional group is a unique fluorinated group that has received a great deal of attention in medicinal chemistry and agrochemistry. However, trifluoromethoxylation of substrates remains a challenging task. Herein we describe the dehydroxytrifluoromethoxylation of alcohols promoted by a RP/ICHCHI (RP = PhP or PhPCH=CH) system in DMF. P-I halogen bonding drives the reaction of RP with ICHCHI in DMF to generate iodophosphonium salt (RPI I) and a Vilsmeier-Haack-type intermediate, both of which could effectively activate alcohols, thus enabling a fast (15 min) trifluoromethoxylation reaction. A wide substrate scope and a high level of functional group tolerance were observed.
CFO官能团是一种独特的氟化基团，在药物化学和农业化学领域受到了广泛关注。然而，底物的三氟甲氧基化仍然是一项具有挑战性的任务。在此，我们描述了在DMF中由RP/ICHCHI（RP = PhP或PhPCH=CH）体系促进的醇的脱羟基三氟甲氧基化反应。P-I卤键驱动RP与ICHCHI在DMF中反应生成碘鎓盐（RPI I）和Vilsmeier-Haack型中间体，这两者都能有效活化醇，从而实现快速（15分钟）的三氟甲氧基化反应。观察到了广泛的底物范围和较高的官能团耐受性。
