Synthesis and ¹⁸F Labeling of Alkenyl Sulfonyl Fluorides via an Unconventional Elimination Pathway

Abstract

A successful Cu-catalyzed addition of both Cl and SO2OCF2H groups into alkenes allows us to discover the unusual reactivity of the SO2OCF2H group. As opposed to common sulfonic esters (RSO2-O-R′), in which the R′ group is highly electrophilic, the SO2 moiety demonstrates higher electrophilicity in RSO2–OCF2H. The unexpected reactivity is further developed not only as a synthetic tool for well-functionalized alkenyl sulfonyl fluorides but also for the first 18F labeling of alkenyl sulfonyl fluorides.

Recent advances in photochemical and electrochemical strategies for the synthesis of sulfonyl fluorides

“…1 Since then, this class of compounds has continued to garner considerable attention from organic chemists and biochemists, particularly after sulfur( vi ) fluoride exchange (SuFEx) came to be regarded as the second-generation click reaction introduced by Sharpless and colleagues in 2014. 2 Sulfonyl fluorides are used to synthesize 3 sulfonamides, 4 sulfones, 5 and sulfonate esters, 6 and in 18 F radiolabelling, 7 and have applications 8 in chemical biology, 9 drug discovery, 10 and materials science. 11 Consequently, numerous methods have been developed for the synthesis of sulfonyl fluorides.…”

Recent Advances of S–18F Radiochemistry for Positron Emission Tomography

“…In addition, it significantly minimizes the required reaction equipment, potentially reducing it to just a heating/stirring aluminum block and disposable vials in the simple setup. Apart from [ 18 F]ESF, the Liang and Xiao groups reported a novel method to get 18 F-labeled alkenesulfonyl fluorides (28) by a three-step reaction 61 (Scheme 8), including Cu-catalyzed addition of Cl/SO 2 OCF 2 H to alkenes (24), dehydrochlorination, and 18 F-labeling of SO 2 OCF 2 H precursor (27) with [ 18 F]fluoride. The unique reactivity exhibited by alkenyl SO 2 OCF 2 H compounds allowed for the convenient radiosynthesis of 18 F-labeled alkenesulfonyl fluorides.…”

Visible-light-driven reactions for the synthesis of sulfur dioxide-inserted compounds: generation of S–F, S–O, and S–N bonds

“…[1][2][3] For example, sulfonyl uoride has been shown to be a useful compound with wide applications in medical sciences, proteomics, and materials science. [4][5][6][7][8][9] Sulfonamides have many applications such as antihypertensive drugs; nonsteroidal anti-inammatory drugs; and as diuretics, anticancer and antibacterial agents, and anticonvulsants. [10][11][12][13][14][15] Sulfone esters are widely employed as anticancer agents, antimicrotubule agents, MAO-A inhibitors, and phosphor-STAT3 inhibitors.…”