Pulikkottil, Feba T., Carvalho, Daniel F., Taniguchi, Kohei, Burnett, John S., Goodall, Charles A. I., Elmes, Victoria K., Hurt, Andrew, Clark, Ewan R. ORCID: https://orcid.org/0000-0001-7287-2631, Meijer, Anthony J. H. M. and Lam, Kevin ORCID: https://orcid.org/0000-0003-1481-9212 (2026) Practical and divergent electrochemical access to thiocarbamoyl fluorides and N-trifluoromethyl amines from secondary amines. Nature Communications. ISSN 2041-1723 (Online) (doi:10.1038/s41467-026-74660-2)

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Abstract

We report a practical and divergent electrochemical method for converting simple secondary amines into thiocarbamoyl fluorides and N-trifluoromethyl amines. Using inexpensive, bench-stable reagents, including Et₃N·3HF and CS₂, these one-pot transformations proceed under mild, open-air conditions without solvent drying, degassing, inert atmosphere, or stoichiometric silver reagents. By tuning the reaction conditions, the same general strategy provides either product class in moderate to excellent yields across a broad substrate scope, with high functional-group tolerance and applicability to late-stage modification of complex bioactive molecules. The method is readily scalable and offers a practical alternative to existing fluorination approaches that rely on hazardous or costly reagents. Mechanistic studies combining cyclic voltammetry, ¹⁹F NMR spectroscopy, UV–Vis spectroscopy, HRMS, XRD, SEM–EDX, authentic intermediate analysis, and DFT calculations support a multistep pathway involving dithiocarbamate salts and thiuram intermediates, followed by bromide-assisted fluorination. This operationally simple, metal-free platform provides practical access to valuable fluorinated nitrogen-containing building blocks for synthesis, medicinal chemistry, and materials science.

Item Type:	Article
Additional Information:	"We are providing an unedited version of this manuscript to give early access to its findings. Before final publication, the manuscript will undergo further editing. Please note there may be errors present which affect the content, and all legal disclaimers apply." - Nature Communications.
Uncontrolled Keywords:	Amine, fluorination, electrosynthesis
Subjects:	Q Science > Q Science (General) T Technology > T Technology (General)
Faculty / School / Research Centre / Research Group:	Faculty of Engineering & Science Faculty of Engineering & Science > School of Science (SCI)
Related URLs:	https://www.nature.com/articles/s41467-0...
Last Modified:	26 Jun 2026 12:18
URI:	https://gala.gre.ac.uk/id/eprint/53836

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