EnT-Mediated N–S Bond Homolysis of a Bifunctional Reagent Leading to Aliphatic Sulfonyl Fluorides

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(4), P. 2364 - 2374

Published: Jan. 18, 2023

Sulfur(VI) fluoride exchange (SuFEx) gives rise to a plethora of high-valent sulfur linkages; however, the availability (aliphatic) sulfonyl manifolds lag behind, owing limited sources introducing SO2F moiety via classical two-electron approach. Recently, radical-based methodologies have emerged as complementary strategy increase diversity accessible click partners. In this work, synthesis bench-stable sulfamoyl reagent is presented, which may undergo sigma-bond homolysis upon visible-light-induced sensitization form protected β-amino fluorides from alkene feedstocks. Notably, offers an appealing access various building blocks for peptido fluorides, relevant in medicinal chemistry context, well intriguing entry β-ammonium sulfonates and β-sultams, alkenes. Densely functionalized 1,3-sultones were obtained by employing allyl alcohols substrates. Surprisingly, chloride-derived β-imino underwent S-O bond formation ring closure yield rigid cyclopropyl sulfonate ester under SuFEx conditions. Furthermore, engaging thiol-based hydrogen atom donor reaction, reactivity same can be tuned toward direct aliphatic fluorides. Mechanistic experiments indicate energy transfer (EnT)-mediated process. The transient radical adds product occurs either radical-radical coupling or (HAT), respectively.

Language: Английский

---

Advances in the construction of diverse SuFEx linkers

National Science Review, Journal Year: 2023, Volume and Issue: 10(6)

Published: April 29, 2023

Abstract Sulfur fluoride exchange (SuFEx), a new generation of click chemistry, was first presented by Sharpless, Dong and co-workers in 2014. Owing to the high stability yet efficient reactivity SVI–F bond, SuFEx has found widespread applications organic synthesis, materials science, chemical biology drug discovery. A diverse collection linkers emerged, involving gaseous SO2F2 SOF4 hubs; SOF4-derived iminosulfur oxydifluorides; O-, N- C-attached sulfonyl fluorides sulfonimidoyl fluorides; novel sulfondiimidoyl fluorides. This review summarizes progress these connectors, with an emphasis on analysing advantages disadvantages synthetic strategies connectors based concept, it is expected be beneficial researchers rapidly correctly understand this field, thus inspiring further development chemistry.

Language: Английский

---

Sulfur fluoride exchange

Nature Reviews Methods Primers, Journal Year: 2023, Volume and Issue: 3(1)

Published: Aug. 3, 2023

Language: Английский

---

Selective Fluorosulfonylation of Thianthrenium Salts Enabled by Electrochemistry

Organic Letters, Journal Year: 2023, Volume and Issue: 25(4), P. 581 - 586

Published: Jan. 25, 2023

A practical electrochemically driven method for fluorosulfonylation of both aryl and alkyl thianthrenium salts has been disclosed. The strategy does not need external redox reagents or metal catalysts. In combination with C-H thianthrenation aromatics, this provides a new tool the site-selective drugs.

Language: Английский

---

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

Green Chemistry, Journal Year: 2024, Volume and Issue: 26(6), P. 3435 - 3440

Published: Jan. 1, 2024

A practical electrosynthesis of aryl sulfonyl fluorides from nitroarenes is described. Cheap N -methylimidazolium p -toluenesulfonate has been found to be an effective additive, promoting the desired fluorosulfonylation under very mild conditions.

Language: Английский

---

Linkage Chemistry of S(VI) Fluorides

Chemistry - A European Journal, Journal Year: 2023, Volume and Issue: 29(33)

Published: March 24, 2023

Sulfur(VI)-fluoride exchange linkage as a next generation of click chemistry was introduced by Sharpless and coworkers in 2014. Distinguished from CuAAC, the SuFEx reaction proceeds under metal-free conditions, reactive linkers are variable, enabling access to diverse class compounds. Therein, series emerged has been widely prevalent fields. The SVI -F bond comparison -Cl features excellent stability chemoselectivity. primarily involves formation S-O S-N bonds via commercially available phenols amines, yet less study on C-SuFEx linkage. This review will focus three types for comprising S-O, S-N, S-C bonds, we hope provide practical guidance chemistry.

Language: Английский

---

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

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(5), P. 3115 - 3127

Published: Feb. 13, 2024

Although the transition metal-catalyzed radical fluorine atom transfer (FAT) strategy has emerged as a powerful tool for construction of C–F bonds, to our knowledge, this approach rarely been applied formation S–F bonds. Here, we report that 4-methoxypyridine 1-oxide can serve an inexpensive and simple yet effective ligand thus promote transformation copper-mediated challengeable FAT sulfonyl radicals, paving way assembly FSO2 group. Based on concept, three Cu(I)-catalyzed protocols involving site-selective intra- intermolecular fluorosulfonylation inert C(sp3)–H bonds 1,2-aminofluorosulfonylation inactivated alkenes have developed, enabling preparation C(sp3)-rich aliphatic fluorides cannot be easily synthesized by known methods. These practical operationally methods result in high functional group tolerance under mild conditions modification bioactive derivatives highly valued molecules. Detailed mechanistic studies indicate unique role facilitating such rare FATs via outer-sphere pathway.

Language: Английский

---

Copper-Catalyzed Chemoselective (Amino)fluorosulfonylation of Hydrocarbons via Intramolecular Fluorine-Atom Transfer

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(6), P. 4318 - 4328

Published: March 6, 2024

Sulfonyl fluorides have found increasing applications as functional molecules in chemistry and biology. We herein report a copper-catalyzed atom-economical access to two categories of sulfonyl through radical relay strategy the presence an SO2 surrogate. The aliphatic C(sp3)–H bond N-fluoro-N-alkyl sulfonamides reacted via 1,5-hydrogen atom transfer (HAT) process, affording alkanesulfonyl with proximal amino group. On other hand, utilizing substrates containing proper C═C double resulted intramolecular olefin aminofluorosulfonylation, allowing synthesis fluorosulfonyl-functionalized pyrrolidines piperidines atom-transfer addition (ATRA). Both reaction systems proceeded under mild conditions, requiring no additional fluorine source. Experimental computational studies suggest that S–F coupling is likely achieved radical-rebound pathway. By taking advantage SuFEx multifunctionality products, method applicable late-stage modification bioactive compounds, drug ligation chemistry, organic synthesis.

Language: Английский

---

Recent Advances in Developing Radical Methods for the Synthesis of Aliphatic Sulfonyl Fluorides

European Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 27(23)

Published: May 25, 2024

Abstract Sulfonyl fluorides have widespread applications in many fields, including organic synthesis, chemical biology, drug discovery and materials science. In particular, the past decade, a number of aliphatic sulfonyl been identified showing various biological activities. These appealing features brought about significant advancement developing synthetic methods to access fluorides. this review, we will discuss recent developments radical approaches for synthesis

Language: Английский

---

Fluorosulfonyl radicals: new horizons for the synthesis of sulfonyl fluorides

Organic Chemistry Frontiers, Journal Year: 2022, Volume and Issue: 9(19), P. 5299 - 5305

Published: Jan. 1, 2022

Recent advances in the generation of fluorosulfonyl radicals toward sulfonyl fluorides are highlighted.

Language: Английский

---