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

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

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Synthesis of Vinyl and 1,3‐Dienyl Sulfones Enabled by Photochemical Excitation of Halogen‐Bonding Complexes

Advanced Synthesis & Catalysis, Год журнала: 2024, Номер 366(6), С. 1422 - 1429

Опубликована: Фев. 1, 2024

Abstract The photochemical catalyst‐free radical‐based synthesis of vinyl and 1,3‐dienyl sulfones is disclosed. Mechanistic investigations support that the transformations rely on a visible‐light‐promoted activation halogen‐bonding complex, which formed between an alkenyl (or 1,3‐dienyl) bromide sodium sulfinate salt. reactions exhibit wide functional group tolerance (compatible with heteroatoms, electron‐withdrawing electron‐donating groups), finding application in structural modification biologically relevant molecules. Eventually, continuous flow protocol was developed to upscale these transformations.

Язык: Английский

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Synthesis of Sulfoximines by Copper-Catalyzed Oxidative Coupling of Sulfinamides and Aryl Boronic Acids

Organic Letters, Год журнала: 2023, Номер 25(42), С. 7656 - 7660

Опубликована: Окт. 12, 2023

A novel copper-catalyzed cross-coupling reaction of sulfinamides and aryl boronic acids is developed. The highly chemoselective stereospecific, which allows mild synthesis optically pure sulfoximines with broad scope functional group tolerance. utility this method demonstrated by the asymmetric pharmaceutical intermediates.

Язык: Английский

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Hydrosulfonylation of Unactivated Alkenes and Alkynes by Halogen-Atom Transfer (XAT) Cleavage of S^VI–F Bond

Organic Letters, Год журнала: 2023, Номер 25(48), С. 8722 - 8726

Опубликована: Ноя. 29, 2023

A photochemical halogen-atom transfer (XAT) method for generating sulfonyl radicals from aryl fluorides has been developed. It allows the hydrosulfonylation of unactivated alkenes, which was challenging to achieve through our previous single-electron route. This reaction excellent functional group tolerance and substrate scope under mild conditions.

Язык: Английский

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Unconventional reactivity of sulfonyl fluorides

Trends in Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Фев. 1, 2025

Язык: Английский

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Unlocking redox-active reactivity of dearomatized pyridines with photochemistry toward meta-C–H functionalization of pyridines

Chem Catalysis, Год журнала: 2025, Номер unknown, С. 101326 - 101326

Опубликована: Март 1, 2025

Язык: Английский

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Mechanochemical Enantiospecific Syntheses of Sulfonimidate Esters and Sulfonimidamides by Various S(VI) Exchange Reactions

ChemistryEurope, Год журнала: 2025, Номер unknown

Опубликована: Март 27, 2025

Mechanochemical S(VI) exchange reactions are developed on chiral S(VI)–F and S(VI)–Cl centers that fast, solvent–free, high–yielding, enantiospecific. This approach is used to synthesize a range of sulfonimidate esters sulfonimidamides from sulfonimidoyl fluorides chlorides under mild reaction conditions. The broad scope this method demonstrated by its successful reactivity with phenols both primary secondary anilines. Furthermore, substitution in 4–nitrophenol‐derived species substituted (SuPhenEx) successfully achieved. faster, greener, reduces the need for formation fluorinated species, while retaining many advantages SuFEx related reactions.

Язык: Английский

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Applications of Sulfonyl Fluorides

Advances in Material Chemistry, Год журнала: 2025, Номер 13(02), С. 161 - 170

Опубликована: Янв. 1, 2025

Язык: Английский

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The Modular Synthesis of Sulfondiimidoyl Fluorides and their Application to Sulfondiimidamide and Sulfondiimine Synthesis

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(38)

Опубликована: Июнь 26, 2024

A modular synthesis of sulfondiimidoyl fluorides-the double aza-analogues sulfonyl fluorides-allowing variation the carbon and both nitrogen-substituents is reported. The chemistry uses readily available organometallic reagents, commercial sulfinylamines, simple electrophiles, N-fluorobenzenesulfonimide (NFSI), as starting materials. reactions are broad in scope, efficient, scalable. We show that fluoride products can be combined with amines to provide sulfondiimidamides, organolithium reagents sulfondiimines, reactivity these transformations modulated by N-substituents.

Язык: Английский

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Enabling Modular Click Chemistry Library through Sequential Ligations of Carboxylic Acids and Amines

Angewandte Chemie International Edition, Год журнала: 2024, Номер unknown

Опубликована: Авг. 19, 2024

Abstract High‐throughput synthesis and screening of chemical libraries play pivotal roles in drug discovery. Click chemistry has emerged as a powerful strategy for constructing highly modular libraries. However, the development new click reactions unlocking clickable building blocks remain exceedingly challenging. Herein, we describe double‐click that enables sequential ligations widely available carboxylic acids amines with fluorosulfuryl isocyanate (FSO 2 NCO) via amidation/SuFEx (sulfur‐fluoride exchange) process. This method provides facile access to N‐fluorosulfonyl amides (RCONHSO F) N‐acylsulfamides NR′R′′) near‐quantitative yields under simple practical conditions. The robustness efficiency this double is showcased by construction 96‐well microtiter plates from large number amines. Preliminary biological activity reveals some compounds exhibit high antimicrobial activities against Gram‐positive bacterium S. aureus drug‐resistant MRSA (MIC up 6.25 μg ⋅ mL −1 ). These results provide compelling evidence potential application library an enabling technology high‐throughput medicinal chemistry.

Язык: Английский

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