Shengchun Wang,Demin Ren,Zhao Liu,Dali Yang,Pengjie Wang,Yiming Gao,Xiaotian Qi &Aiwen Lei.Nature Synthesis.（雷爱文）

Abstract：

        Developing practical strategies to produce high-value chemicals, such as pharmacologically active molecules, from bulk starting materials is an ongoing challenge. One potential route to this goal is the C(sp3)–H fluoroalkylation of natural products, made possible by the unique physiological properties of fluorine-containing groups. However, protocols for such fluoroalkylation remain underdeveloped. Here we report a method for the site-selective allylic fluoroalkylation of olefins through a cobalt-catalysed process comprising halogen-atom transfer and hydrogen-atom transfer. This low-cost and operationally simple protocol is readily scalable to a 2 mol scale under mild conditions. Mechanistic studies indicate that both the cobaloxime catalyst and N,N-diisopropylethylamine are essential for producing fluoroalkyl radicals. Density functional theory calculations reveal that the observed site-selectivity is controlled by steric hindrance in the cobalt-promoted hydrogen-atom transfer step.      

        论文链接：https://www.nature.com/articles/s44160-023-00365-9