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Updated: Sep 23, 2025

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Nucleophilic Fluorination Catalyzed by a Cyclometallated Rhodium Complex
Patrick J Morgan1, Graham C Saunders2, Stuart A Macgregor3
1GSK Carbon Neutral Laboratory, School of Chemistry, University of Nottingham, Nottingham NG7 2TU, U.K.
Abstract:
Quantitative catalytic nucleophilic fluorination of a range of acyl chlorides to acyl fluorides was promoted by a cyclometallated rhodium complex [(η5,κ2C-C5Me4CH2C6F5CH2NC3H2NMe)- RhCl] (1). 1 can be prepared in high yields from commercially available starting materials using a one-pot method. The catalyst could be separated, regenerated, and reused. Rapid quantitative fluorination generated the fluoride analogue of the active pharmaceutical ingredient probenecid. Infrared in situ monitoring verified the clean conversion of the substrates to products. VTNA graphical kinetic analysis and DFT calculations lead to a postulated reaction mechanism involving a nucleophilic Rh-F bond.
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