WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, 295 Cathedral Street, Glasgow, G1 1XL, UK.
Chemistry, School of Natural and Environmental Sciences, Newcastle University, Newcastle upon Tyne, NE1 7RU, UK.
Angew Chem Int Ed Engl. 2018 Jan 2;57(1):187-191. doi: 10.1002/anie.201709750. Epub 2017 Nov 30.
Pairing iron bis(amide) Fe(HMDS) with Na(HMDS) to form new sodium ferrate base [(dioxane) ⋅NaFe(HMDS) ] (1) enables regioselective mono and di-ferration (via direct Fe-H exchange) of a wide range of fluoroaromatic substrates under mild reaction conditions. Trapping of several ferrated intermediates has provided key insight into how synchronised Na/Fe cooperation operates in these transformations. Furthermore, using excess 1 at 80 °C switches on a remarkable cascade process inducing the collective twofold C-H/threefold C-F bond activations, where each C-H bond is transformed to a C-Fe bond whereas each C-F bond is transformed into a C-N bond.
将铁双（酰胺）Fe（HMDS）与 Na（HMDS）配对形成新的高铁酸钠基[(二氧杂环己烷)·NaFe（HMDS）]（1），可在温和的反应条件下对各种氟代芳烃底物进行区域选择性的单和二取代（通过直接 Fe-H 交换）。几种高铁酸盐中间体的捕获为理解 Na/Fe 协同作用在这些转化中的如何协同作用提供了关键见解。此外，在 80°C 下使用过量的 1 可启动一个显著的级联过程，诱导协同的双重 C-H/三重 C-F 键活化，其中每个 C-H 键转化为 C-Fe 键，而每个 C-F 键转化为 C-N 键。
