A Quantitative Reactivity Scale for Electrophilic Fluorinating Reagents

Rozatian, Neshat; Ashworth, Ian W.; Sandford, Graham; Hodgson, David R.W.

Abstract

Electrophilic N-F fluorination agents underpin the introduction of fluorine in aliphatic systems across drug and academic research. The choice of N-F reagent is currently determined through empirical experimentation in the absence of quantitative values for electrophilicities. Here we report an experimentally-determined kinetic reactivity scale for ten N-F fluorinating reagents, including Selectfluor™, NFSI, Synfluor™ and several N-fluoropyridinium salts, in acetonitrile. The reactivity scale, which covers eight orders of magnitude, employs para-substituted 1,3-diaryl-1,3-dicarbonyl derivatives to measure relative and absolute rate constants. The para-substituted 1,3-diaryl-1,3-dicarbonyl scaffold delivers a convenient, sensitive spectrophotometric reporter of reactivity that also led to the discovery of a unique form of tautomeric polymorphism.

Citation

Rozatian, N., Ashworth, I. W., Sandford, G., & Hodgson, D. R. (2018). A Quantitative Reactivity Scale for Electrophilic Fluorinating Reagents. Chemical Science, 9(46), 8692-8702. https://doi.org/10.1039/c8sc03596b

• Journal Article Type: Article
• Acceptance Date: Sep 13, 2018
• Online Publication Date: Sep 14, 2018
• Publication Date: Dec 14, 2018
• Deposit Date: Sep 14, 2018
• Publicly Available Date: Nov 29, 2018
• Journal: Chemical Science
• Print ISSN: 2041-6520
• Electronic ISSN: 2041-6539
• Publisher: Royal Society of Chemistry
• Peer Reviewed: Peer Reviewed
• Volume: 9
• Issue: 46
• Pages: 8692-8702
• DOI: https://doi.org/10.1039/c8sc03596b
• Public URL: https://durham-repository.worktribe.com/output/1314655