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

Abstract

This review summarizes the latest achievements in photochemical and electrochemical strategies for the synthesis of sulfonyl fluorides and focuses on the novel features and proposed mechanisms.

Direct electrochemical synthesis of arenesulfonyl fluorides from nitroarenes: a dramatic ionic liquid effect

“…On the basis of the above-described results and previous reports, 11–15,19 two plausible mechanisms have been proposed (Fig. 1).…”

“…4 Aryl sulfonyl fluorides are typically synthesized by chloride–fluoride exchange reactions of the corresponding arenesulfonyl chlorides, 5 oxidative fluorination of sulfur-containing substrates (such as sodium sulfinic, 6 thiols, 7 sulfonyl hydrazides, 8 disulfides, 7 b ,9 and sulfonates or sulfonic acids 10 ) or by converting various prefunctionalized substrates such as aryl (pseudo)halides, 11 aryl boronic acids, 12 aryl diazonium salts, 13 and others. 14 Despite these advances, the development of practical, mild methods for accessing arenesulfonyl fluorides from inexpensive, widely available industrial feedstocks remains highly desirable.…”

Copper-Mediated Radical Fluorine-Atom Transfer to Sulfonyl Radical: A Dramatic 4-Methoxypyridine 1-Oxide Ligand Effect

“…As one of the key elements in drug discovery, agrochemicals, pharmaceuticals, materials, and click chemistry (such as sulfonyl fluorides), fluorine has become increasingly important in recent decades, and has promoted the development of many new methods for the efficient synthesis of versatile fluoro-containing molecules, especially in a site-selective manner . While many successful methods for constructing the C–F bond often rely on the use of nucleophilic or electrophilic fluorination strategies, the transition metal-catalyzed radical fluoro atom transfer (FAT) process to suitable carbon-based radicals has emerged as a powerful way to connect a fluoro atom with a carbon chain. Some metals such as Mn, Ag, Fe, Pd, Cu and Co have been reported for this purpose (Figure A).…”

Green and Efficient Protocols for the Synthesis of Sulfonyl Fluorides Using Potassium Fluoride as the Sole Fluorine Source

“…This interplay between the reactivity and stability of these chemical entities makes them well-suited for a wide range of biochemical and material-based applications such as irreversible enzyme inhibitors, ,, 18 F-radiolabeling agents, − and deoxy-fluorinating agents. − Furthermore, sulfonyl fluorides have been employed to modify polymers; enhance their solubility, stability, and reactivity; and develop novel materials for organic electronics (Scheme A). , The synthesis of sulfonyl fluorides is of paramount importance given their demonstrated value. It is imperative to develop an efficient synthetic route that employs readily available, abundant, and stable starting materials while circumventing the use of hazardous, toxic, or expensive reagents. − Various synthetic approaches have been introduced starting from the fluorosulfonylation of aromatic arenes using fluorosulfonic acid, dating back almost a century . The development of this approach has been ongoing, with different variations in reagents (gaseous sulfuryl fluoride or fluorosulfonic acid anhydride) and substrates (Grignard reagents or lithiated alkynes). − …”