Overcoming a Radical Polarity Mismatch in Strain‐Release Pentafluorosulfanylation of [1.1.0]Bicyclobutanes: An Entryway to Sulfone‐ and Carbonyl‐Containing SF₅‐Cyclobutanes

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(19)

Published: Jan. 18, 2024

The first assortment of achiral pentafluorosulfanylated cyclobutanes (SF

Language: Английский

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(Hetero)aryl‐S^VI Fluorides: Synthetic Development and Opportunities

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(23)

Published: March 18, 2022

(Hetero)arylsulfur compounds where the S atom is in oxidation state VI represent a large percentage of molecular functionalities present organic chemistry. More specifically, (hetero)aryl-S

Language: Английский

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Metal‐Free SF₆Activation: A New SF₅‐Based Reagent Enables Deoxyfluorination and Pentafluorosulfanylation Reactions

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(27)

Published: April 26, 2022

The activation of SF6 , a potent greenhouse gas, under metal-free and visible light conditions is reported. Herein, mechanistic investigations including EPR spectroscopy, NMR studies cyclic voltammetry allowed the rational design new fluorinating reagent which was synthesized from 2-electron with commercially available TDAE. This SF5 -based efficiently employed for deoxyfluorination CO2 fluorinative desulfurization CS2 allowing formation useful fluorinated amines. Moreover, first time we demonstrated that our could afford mild generation Cl-SF5 gas. finding exploited chloro-pentafluorosulfanylation alkynes alkenes.

Language: Английский

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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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Strain‐Release Pentafluorosulfanylation and Tetrafluoro(aryl)sulfanylation of [1.1.1]Propellane: Reactivity and Structural Insight**

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(48)

Published: Sept. 22, 2022

We leveraged the recent increase in synthetic accessibility of SF

Language: Английский

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The Linkage of Sulfonimidoyl Fluorides and Unactivated Alkenes via Hydrosulfonimidoylation

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(44)

Published: Sept. 15, 2022

Abstract Sulfur(VI) fluoride cleavage and exchanging linkage, a new generation of linkage chemistry, exhibits enormous potential for combining range functional molecules in an increasing number fields. Herein, we established metal‐free unactivated alkenes sulfonimidoyl fluorides via hydrosulfonimidoylation to construct sulfoximines within minutes. An intermolecular hydride transfer process is the key step, it occurs overlap LUMO cation HOMO alkene, which was confirmed control experiments with deuterated compounds. DFT calculations further demonstrated concerted involving formation S−C( sp 3 ) bond transfer. Remarkably, abundant natural products pharmaceuticals multiple heteroatoms sensitive groups have been subjected current reaction achieve various sulfoximine linkages, furnishing basis drug discovery conjugation.

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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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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Regio‐ and Stereoselective Hydroelementation of SF₅‐Alkynes and Further Functionalizations.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(19)

Published: March 9, 2023

Herein is described a fully regio- and stereoselective hydroelementation reaction of SF5 -alkynes with N, O S-nucleophiles further functionalization the corresponding Z-(hetero)vinyl-SF5 intermediates, suitable platform to access α-SF5 ketones esters, β-SF5 amines alcohols under mild conditions. Experimental computational comparative studies between - CF3 have been performed highlight explain difference reactivity selectivity observed these two fluorinated motifs.

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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