Utilising sodium-mediated ferration for regioselective functionalisation of fluoroarenes via C-H and C-F bond activations

Maddock, Lewis C. H. and Nixon, Tracy and Kennedy, Alan R. and Probert, Michael R. and Clegg, William and Hevia, Eva (2017) Utilising sodium-mediated ferration for regioselective functionalisation of fluoroarenes via C-H and C-F bond activations. Angewandte Chemie International Edition, 57 (1). pp. 187-191. ISSN 1433-7851

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    Abstract

    Pairing iron bis(amide) Fe(HMDS)2 with Na(HMDS) to form new sodium ferrate base [(dioxane)0.5·NaFe(HMDS)3] (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 80oC switches on a remarkable cascade process inducing the collective 2-fold C-H/3-fold 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.