Radical Hydro‐Fluorosulfonylation of Unactivated Alkenes and Alkynes

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(39)

Published: Aug. 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.

Language: Английский

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Aliphatic sulfonyl fluoride synthesis via reductive decarboxylative fluorosulfonylation of aliphatic carboxylic acid NHPI esters

Organic Chemistry Frontiers, Journal Year: 2022, Volume and Issue: 9(4), P. 1115 - 1120

Published: Jan. 1, 2022

A general and efficient approach to various aliphatic sulfonyl fluorides by the reductive decarboxylative fluorosulfonylation of carboxylic acids via a radical sulfur dioxide insertion fluorination strategy was developed.

Language: Английский

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Electrochemical Synthesis of β-Keto Sulfonyl Fluorides via Radical Fluorosulfonylation of Vinyl Triflates

Organic Letters, Journal Year: 2022, Volume and Issue: 24(20), P. 3702 - 3706

Published: May 17, 2022

Electrochemical synthesis of versatile β-keto sulfonyl fluorides is accomplished by radical fluorosulfonylation vinyl triflates with FSO2Cl as the fluorosulfonyl source. This electroreductive protocol uses inexpensive graphite felt electrodes, thus avoiding use a sacrificial anode. Moreover, this protocol, featuring metal-free, mild conditions and easy scalability, allows expedient access to valuable from readily available precursors, well cyclic ones that are otherwise inaccessible using prior methods.

Language: Английский

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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

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Phosphorus fluoride exchange: Multidimensional catalytic click chemistry from phosphorus connective hubs

Chem, Journal Year: 2023, Volume and Issue: 9(8), P. 2128 - 2143

Published: June 7, 2023

Language: Английский

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Radical Fluorosulfonyl Heteroarylation of Unactivated Alkenes with Quinoxalin-2(1H)-ones and Related N-Heterocycles

Organic Letters, Journal Year: 2023, Volume and Issue: 25(7), P. 1088 - 1093

Published: Feb. 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.

Language: Английский

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Photocatalytic Sulfonyl Fluorination of Alkyl Organoboron Substrates

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(6), P. 3668 - 3675

Published: Feb. 28, 2023

Sulfonyl fluorides are highly versatile molecules for click chemistry that have found applications in many areas of and biology. Recent chemical approaches focused on the synthesis alkyl sulfonyl from readily available starting materials. Here, we report a photocatalytic organotrifluoroborates boronic acid pinacol esters, which building blocks commonly employed by medicinal chemists bioactive molecules. Steady-state time-resolved spectroscopy confirmed absorption photons acridinium catalysts leads to oxidation organotrifluoroborate substrates. The reaction exhibits broad functional group tolerance, can be attributed mild activation with visible light. Importantly, this general approach provides easy access primary, secondary, tertiary fluorides.

Language: Английский

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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

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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

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Base-Free SuFEx Reaction Promoted by Silica Gel for the Synthesis of β-Sultams

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 6, 2025

β-Sultams are recognized as potential antibacterial agents and crucial building blocks in chemical synthesis. Herein, a "SuFEx on silica gel" approach has been developed for one-step synthesis of β-sultams utilizing readily available amines ethenesulfonyl fluoride (ESF). This process involves sequential Michael addition to ESF, followed by an intramolecular SuFEx reaction promoted gel. Silica gel facilitates the activation sulfonyl through hydrogen bonding between SVI-F surface hydroxyl groups eliminates HF formed during reaction. Notably, use base, which is typically required nearly all known reactions, was rendered unnecessary. The β-sultam moiety successfully incorporated into 26 tested primary amines, including pharmaceuticals natural products, high yields, showcasing broad applications this method.

Language: Английский

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