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.
- mixed-metal chemistry
- C-F bond activation
- cascade processes
Maddock, L. C. H., Nixon, T., Kennedy, A. R., Probert, M. R., Clegg, W., & Hevia, E. (2017). Utilising sodium-mediated ferration for regioselective functionalisation of fluoroarenes via C-H and C-F bond activations. Angewandte Chemie International Edition, 57(1), 187-191. https://doi.org/10.1002/anie.201709750