Electrochemically promoted defluorinative sulfoximination and fluorosulfonylation of non-activated aryl fluorides at room temperature

Abstract

Due to the high bond dissociation energy and kinetic inertness of the C–F bond, direct activation of inert aryl fluorides for new transformations under mild conditions remains a significant challenge. Although it has been known that single electron reduction can be applied for the activation of inert aryl fluorides at room temperature, the need for very strong reduction conditions along with the competitive side reactions during the reduction process limits the synthetic applications. Herein, by leveraging the advantages of electrosynthesis and the versatile transformation nature of aryl radicals, two types of challenging defluorinative transformations of non-activated aryl fluorides which include sulfoximination via cheap nickel catalysis and transition metal catalyst-free fluorosulfonylation at room temperature have been disclosed for the first time. These reactions show good functional group tolerance and can be applied for the late-stage modifications of bioactive derivatives. As for the practical nickel-catalyzed defluorinative sulfoximination, detailed mechanistic studies reveal that after the cathodic reduction of aryl fluorides to form the key aryl radical, subsequent nickel-promoted C–N bond formation via paired electrolysis is responsible for the success.

Graphical abstract: Electrochemically promoted defluorinative sulfoximination and fluorosulfonylation of non-activated aryl fluorides at room temperature

Supplementary files

Article information

Article type
Edge Article
Submitted
21 May 2025
Accepted
30 Jun 2025
First published
01 Jul 2025
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2025, Advance Article

Electrochemically promoted defluorinative sulfoximination and fluorosulfonylation of non-activated aryl fluorides at room temperature

X. Kong, Y. Chen, S. Zhang, K. Feng, X. Chen, L. Dong, M. Li, Y. Xu and Z. Cao, Chem. Sci., 2025, Advance Article , DOI: 10.1039/D5SC03674G

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