Nucleophilic Fluorination Catalyzed by a Cyclometallated Rhodium Complex

Morgan, Patrick J.; Saunders, Graham C.; Macgregor, Stuart A.; Marr, Andrew C.; Licence, Peter

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.

• Journal Article Type: Article
• Acceptance Date: Mar 22, 2022
• Online Publication Date: Mar 31, 2022
• Publication Date: Apr 11, 2022
• Deposit Date: Mar 25, 2022
• Publicly Available Date: Apr 1, 2023
• Journal: Organometallics
• Print ISSN: 0276-7333
• Electronic ISSN: 1520-6041
• Publisher: American Chemical Society (ACS)
• Peer Reviewed: Peer Reviewed
• Volume: 41
• Issue: 7
• Pages: 883–891
• DOI: https://doi.org/10.1021/acs.organomet.2c00052
• Keywords: Inorganic Chemistry; Organic Chemistry; Physical and Theoretical Chemistry
• Public URL: https://nottingham-repository.worktribe.com/output/7650543
• Publisher URL: https://pubs.acs.org/doi/abs/10.1021/acs.organomet.2c00052
• Additional Information: This document is the Accepted Manuscript version of a Published Work that appeared in final form in Organometallics, copyright© American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://pubs.acs.org/doi/abs/10.1021/acs.organomet.2c00052