Effect of Nucleophile Deprotonation on SuFEx: Synthesis of Sulfonamides DOI
J. Dudzinski,

Jacek Bochra,

Michał Barbasiewicz

et al.

Synthesis, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 21, 2024

Abstract In a quest for efficient SuFEx-type transformations we studied reactions of amines with 4-fluorobenzenesulfonyl fluoride. The substrate may react by fluoride substitution at the aromatic ring (SNAr) and sulfonyl group (SuFEx). Analysis reaction course revealed that deprotonation N-nucleophile controls course: neutral in DMF attack ring, whereas amine anions, generated equilibrium LiHMDS toluene, favor substitution. Using base-promoted conditions synthesized set substituted sulfonamides high yields.

Language: Английский

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

Xinshu Qin,

Minlong Wang,

Jiaman Hou

et al.

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

Citations

1
Mechanochemical Enantiospecific Syntheses of Sulfonimidate Esters and Sulfonimidamides by Various S(VI) Exchange Reactions DOI Creative Commons

Shubhangi Tripathi,

Sidharam P. Pujari,

Marjorie Romkes

et al.

ChemistryEurope, Journal Year: 2025, Volume and Issue: unknown

Published: March 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.

Language: Английский

Citations

0
The Modular Synthesis of Sulfondiimidoyl Fluorides and their Application to Sulfondiimidamide and Sulfondiimine Synthesis DOI Creative Commons
Mingyan Ding,

Charles Bell,

Michael C. Willis

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(38)

Published: June 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.

Language: Английский

Citations

3
Mechanochemical Iron‐Catalyzed Nitrene Transfer Reactions: Direct Synthesis of N‐Acyl Sulfonimidamides from Sulfinamides and Dioxazolones DOI Creative Commons

Shulei Pan,

Florian F. Mulks, Peng Wu

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 63(5)

Published: Dec. 7, 2023

A mechanochemical synthesis of sulfonimidamides by iron(II)-catalyzed exogenous ligand-free N-acyl nitrene transfer to sulfinamides is reported. The one-step method tolerates a wide range with various substituents under solvent-free ambient conditions. Compared its solution-phase counterpart, this approach shows better conversion and chemoselectivity. Mechanistic investigations ESI-MS revealed the generation crucial iron intermediates.

Language: Английский

Citations

9
2‐Methylimidazole‐1‐(N‐tert‐octyl)sulfonimidoyl Fluoride: A Bench‐Stable Alternative to SOF4 as Precursor to N,O‐Substituted S(VI) Compounds DOI Creative Commons
Natassa Lional, Fedor M. Miloserdov, Han Zuilhof

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(36)

Published: June 10, 2024

S(VI) compounds with multiple N or O substituents are often difficult to make and several crucial routes, such as multimodal SuFEx (Sulfur (VI) Fluoride Exchange) chemistry, rely on the highly useful but hazardous SOF

Language: Английский

Citations

2
Enantioselective Synthesis of Chiral Sulfonimidoyl Fluorides Facilitates Stereospecific SuFEx Click Chemistry DOI

He-sen Huang,

Yi Yuan, Wei Wang

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 5, 2024

Abstract Sulfur‐centered electrophilic ‘warheads’ have emerged as key components for chemical proteomic probes through sulfur‐exchange chemistry (SuFEx) with protein nucleophiles. Among these functional groups, sulfonimidoyl fluorides (SIFs) stand out their modifiable sites, tunable electrophilicities, and chiral sulfur‐center, presenting exciting possibilities new covalent probes. However, the synthetic access to SIFs has been a challenge, limiting exploration applications. In this study, we describe convenient route obtain from readily available sulfenamides via series of one‐pot tandem reactions high enantiomeric excess (ees). The resulting were further converted into diverse array S(VI) derivatives under mild conditions or in buffer solutions. Most significantly, specificity ligation experiments underscored critical role sulfur‐center chirality design screening more‐selective therapeutics.

Language: Английский

Citations

2
Lewis Acid-Catalyzed Sulfur Fluoride Exchange DOI Creative Commons

Theodore D. Yassa,

Yuxin Fang,

Lana K. Ravelo

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(46), P. 9897 - 9902

Published: Nov. 9, 2024

A new method uses metal Lewis acids as catalysts to convert sulfonyl fluorides, fluorosulfates, and sulfamoyl fluorides with silyl amines into S-N bond-containing compounds via sulfur fluoride exchange. The reaction successfully employs Ca(NTf

Language: Английский

Citations

2
Mechanochemical Iron‐Catalyzed Nitrene Transfer Reactions: Direct Synthesis of N‐Acyl Sulfonimidamides from Sulfinamides and Dioxazolones DOI Creative Commons

Shulei Pan,

Florian F. Mulks, Peng Wu

et al.

Angewandte Chemie, Journal Year: 2023, Volume and Issue: 136(5)

Published: Dec. 6, 2023

Abstract A mechanochemical synthesis of sulfonimidamides by iron(II)‐catalyzed exogenous ligand‐free N ‐acyl nitrene transfer to sulfinamides is reported. The one‐step method tolerates a wide range with various substituents under solvent‐free ambient conditions. Compared its solution‐phase counterpart, this approach shows better conversion and chemoselectivity. Mechanistic investigations ESI‐MS revealed the generation crucial iron intermediates.

Language: Английский

Citations

4
N-Heterocyclic carbene-catalyzed silicon-free sulfur fluoride exchange reactions of sulfonimidoyl fluorides DOI Creative Commons

Muze Lin,

Yu Xie, Shuangjun Li

et al.

Published: Feb. 14, 2024

As the monoaza analogous of sulfonates and sulfonamides, sulfonimidate ester sulfonimidamide have attracted growing attention in recent years. In this paper. We report an organocatalytic silicon-free sulfur fluoride exchange (SuFEx) reaction sulfonimidoyl fluorides for synthesis these valuable organosulfurs. Under catalysis 10 mol% N-heterocyclic carbene (NHC), MS 4Å, reacted with phenols to produce esters 55-99% yields. addition, under relay NHC HOBt, various amines coupled give sulfonimidamides

Language: Английский

Citations

1
2‐Methylimidazole‐1‐(N‐tert‐octyl)sulfonimidoyl Fluoride: A Bench‐Stable Alternative to SOF4 as Precursor to N,O‐Substituted S(VI) Compounds DOI Creative Commons
Natassa Lional, Fedor M. Miloserdov, Han Zuilhof

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(36)

Published: June 10, 2024

Abstract S(VI) compounds with multiple N or O substituents are often difficult to make and several crucial routes, such as multimodal SuFEx (Sulfur (VI) Fluoride Exchange) chemistry, rely on the highly useful but hazardous SOF 4 gas. Safety issues inaccessibility of strongly hamper developments these organic compounds. Here we describe synthesis applications 2‐methyl im idazole‐1‐( ‐ tert ‐octyl) s ulfonimidoyl f luoride (ImSF), a novel bench‐stable analogue . ImSF is synthesized gram scale via double fluorination t ‐OctNSO. We show can undergo substitution reactions phenols amines, which lead sulfurimidates sulfuramidimidates, respectively, intrinsically chiral analogous medicinally relevant sulfates sulfamates in an S=O moiety replaced by S=NR unit. Finally demonstrate that substitutions occur enantiospecifically, providing first entry sulfuramidimidates.

Language: Английский

Citations

1