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Combining a bulky bis(amide) and a reactive one-coordinate TMP (2,2,6,6-tetramethylpiperidide) ligand, a new mixed K/Zn heteroleptic base has been developed for regioselective zincation of fluoroarenes. This special ligand set allows for trapping and structural authentication of the first intermediates of direct Zn–H exchange of fluoroarenes obtained via deprotonative metallation, providing mechanistic insights of the processes involved.

Graphical abstract: Metallation of sensitive fluoroarenes using a potassium TMP-zincate supported by a silyl(bis)amido ligand

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