Trends in Chemistry, Год журнала: 2025, Номер unknown
Опубликована: Янв. 1, 2025
Язык: Английский
Journal of the American Chemical Society, Год журнала: 2023, Номер 145(4), С. 2364 - 2374
Опубликована: Янв. 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.
Язык: Английский
Процитировано
91
National Science Review, Год журнала: 2023, Номер 10(6)
Опубликована: Апрель 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.
Язык: Английский
Процитировано
69
Organic & Biomolecular Chemistry, Год журнала: 2023, Номер 21(7), С. 1356 - 1372
Опубликована: Янв. 1, 2023
This review highlights key advances in the synthesis and biomolecular applications of sulfur( vi )-fluorides.
Язык: Английский
Процитировано
48
Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(39)
Опубликована: Авг. 9, 2022
Abstract Recently, radical fluorosulfonylation is emerging as an appealing approach for the synthesis of sulfonyl fluorides, which are highly in demand various disciplines, particularly chemical biology and drug discovery. Here, we report first establishment hydro‐fluorosulfonylation alkenes, enabled by using 1‐fluorosulfonyl 2‐aryl benzoimidazolium (FABI) effective redox‐active precursor. This method provides a new facile aliphatic fluorides from unactivated can be further applied to late‐stage modifications natural products peptides, well ligation drugs combination with click chemistry. Remarkably, this system could enable alkynes, affording valuable alkenylsulfonyl fluoride rare, high Z ‐selectivity, normally less stable more challenging synthesize comparison E ‐configured products.
Язык: Английский
Процитировано
54
Chemistry - A European Journal, Год журнала: 2023, Номер 29(33)
Опубликована: Март 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.
Язык: Английский
Процитировано
38
Organic Letters, Год журнала: 2023, Номер 25(7), С. 1088 - 1093
Опубликована: Фев. 13, 2023
The incorporation of sulfonyl fluoride groups into molecules has been proved effective to enhance their biological activities or introduce new functions. Herein, we report a transition-metal-free and visible-light-mediated radical 1-fluorosulfonyl-2-heteroarylation alkenes, which could allow access series SO2F-containing quinoxalin-2(1H)-ones, are critical structural motif widely present in number biologically active molecules. Further application the method modification other heterocycles drug as well ligation chemistry via SuFEx click reactions is also demonstrated.
Язык: Английский
Процитировано
31
ACS Catalysis, Год журнала: 2024, Номер 14(6), С. 4318 - 4328
Опубликована: Март 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.
Язык: Английский
Процитировано
11
European Journal of Organic Chemistry, Год журнала: 2024, Номер 27(23)
Опубликована: Май 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
Язык: Английский
Процитировано
11
Organic Chemistry Frontiers, Год журнала: 2022, Номер 9(19), С. 5299 - 5305
Опубликована: Янв. 1, 2022
Recent advances in the generation of fluorosulfonyl radicals toward sulfonyl fluorides are highlighted.
Язык: Английский
Процитировано
29
Nature Communications, Год журнала: 2023, Номер 14(1)
Опубликована: Авг. 24, 2023
Sulfonyl and sulfonimidoyl fluorides are versatile substrates in organic synthesis medicinal chemistry. However, they have been exclusively used as S(VI)+ electrophiles for defluorinative ligations. Converting sulfonyl to S(VI) radicals is challenging underexplored due the strong bond dissociation energy of SVI-F high reduction potentials, but once achieved would enable dramatically expanded synthetic utility downstream applications. In this report, we disclose a general platform address issue through cooperative organosuperbase activation photoredox catalysis. Vinyl sulfones sulfoximines obtained with excellent E selectivity under mild conditions by coupling reactions alkenes. The method preparation functional polymers dyes also demonstrated.
Язык: Английский
Процитировано
20