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 to deliver iodoferrocene derivatives faster than using classical solvents. Various N, O, P and C-nucleophiles were found compatible with this transformation which occurs with full retention of stereochemistry. Original P,N-ligands were prepared by using iodine/lithium exchange-chlorophoshine trapping sequences, and their properties were evaluated in Suzuki-Miyaura and Buchwald-Hartwig coupling as well as in ketone alpha-arylation reaction.