HFIP‐Promoted Substitution in the Ferrocene Series: Smooth Approach towards Original Catalysts**

Pseudo-benzylic substitution is an important reaction in the ferrocene series, especially to obtain ligands for catalysis. Herein, we described new reactions conditions, using fluorinated alcohols as both solvent and promoter, able deliver iodoferrocene derivatives faster than classical solvents. Various N, O, P C-nucleophiles were found compatible with this transformation which occurs full retention of stereochemistry. Original P,N-ligands prepared by iodine/lithium exchange-chlorophoshine trapping sequences, their properties evaluated Suzuki-Miyaura Buchwald-Hartwig coupling well ketone α-arylation reaction.