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

Enantioselective sulfur(VI) fluoride exchange reaction of iminosulfur oxydifluorides DOI
Zhiyuan Peng, Shoujun Sun, Meng‐Meng Zheng

et al.

Nature Chemistry, Journal Year: 2024, Volume and Issue: 16(3), P. 353 - 362

Published: Feb. 14, 2024

Language: Английский

Citations

23
C-SuFEx linkage of sulfonimidoyl fluorides and organotrifluoroborates DOI Creative Commons

Suqin Zhao,

Daming Zeng,

Ming Wang

et al.

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Jan. 25, 2024

Abstract Sulfur(VI) fluoride exchange, a new type of linkage reaction, has excellent potential for application in functional molecule to prepare pharmaceuticals, biomolecules, and polymers. Herein, C-SuFEx reaction is established achieve fast (in minutes) between sulfonimidoyl fluorides aryl/alkyl organotrifluoroborates. Potassium organotrifluoroborates are instantaneously activated via substoichiometric amount trimethylsilyl triflate afford organodifluoroboranes, releasing BF 3 as an activating reagent situ. This sulfur(VI) exchange technique capable forming S(VI)-C(alkyl), S(VI)-C(alkenyl) S(VI)-C(aryl) bonds, demonstrating its broad scope. Natural products pharmaceuticals with sensitive groups, such valdecoxib, celecoxib diacetonefructose, compatible this protocol, allowing the formation diverse sulfoximines.

Language: Английский

Citations

14
Strain-promoted S-arylation and alkenylation of sulfinamides using arynes and cyclic alkynes DOI
Xi Zou,

Boming Shen,

Gaolin Li

et al.

Science China Chemistry, Journal Year: 2024, Volume and Issue: 67(3), P. 928 - 935

Published: Jan. 15, 2024

Language: Английский

Citations

11
Copper-Catalyzed Chemoselective (Amino)fluorosulfonylation of Hydrocarbons via Intramolecular Fluorine-Atom Transfer DOI

Shuting Qu,

Xiao‐Xi Li, Xingwei Li

et al.

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

Citations

11
Recent Advances in Developing Radical Methods for the Synthesis of Aliphatic Sulfonyl Fluorides DOI

Lu Lin,

Guanhua Pei,

Zhong‐Yan Cao

et al.

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

Citations

11
Post-polymerization functionalization of aliphatic polycarbonates using click chemistry DOI Creative Commons
Mohsan Hassan, Gulzar A. Bhat, Donald J. Darensbourg

et al.

Polymer Chemistry, Journal Year: 2024, Volume and Issue: 15(18), P. 1803 - 1820

Published: Jan. 1, 2024

Presently there is much interest in the synthesis of degradable, more sustainable polymers from resources that minimize use petroleum-based feedstocks.

Language: Английский

Citations

8
Poly(vinyl chloride) (PVC): an updated review of its properties, polymerization, modification, recycling, and applications DOI
Great Iruoghene Edo, Winifred Ndudi,

Ali B. M. Ali

et al.

Journal of Materials Science, Journal Year: 2024, Volume and Issue: 59(47), P. 21605 - 21648

Published: Nov. 27, 2024

Language: Английский

Citations

8
Intramolecular Friedel–Crafts Reactions of Sulfamoyl Fluorides, Fluorosulfates, and Sulfuramidimidoyl Fluorides DOI
Taijie Guo, Long Xu, Jiajia Dong

et al.

Organic Letters, Journal Year: 2025, Volume and Issue: 27(6), P. 1356 - 1361

Published: Jan. 30, 2025

Sultams are valuable heterocycles with numerous applications, particularly as pharmacophores. Previous syntheses of these compounds usually require metal-catalyzed cyclization or multiple-step processes. Here, we report a straightforward strategy for accessing important motifs by developing the intramolecular Friedel-Crafts sulfamoyl fluorides under mild conditions. Our protocol also accommodates fluorosulfates and sulfuramidimidoyl fluorides, which rarely utilized in reactions.

Language: Английский

Citations

1
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
Turning sulfonyl and sulfonimidoyl fluoride electrophiles into sulfur(VI) radicals for alkene ligation DOI Creative Commons
Wu Xing, Wenbo Zhang,

Guangwu Sun

et al.

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: Aug. 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.

Language: Английский

Citations

20