The Shuttle of Sulfur Dioxide: Iridium/Copper‐Cocatalyzed Trifluoromethylfluorosulfonylation of Alkenes DOI

Yifei Yang,

Fang Xiao, Jin‐Hong Lin

et al.

Advanced Synthesis & Catalysis, Journal Year: 2023, Volume and Issue: 365(3), P. 301 - 306

Published: Jan. 11, 2023

Abstract Depending on the nature of attached functional moiety, sulfonyl radical can either undergo an automatic SO 2 liberation or react directly as thermodynamically favored radical. Taking advantage this unique property, we envisioned that through rational reaction design, in situ release and re‐insertion , i. e., shuttle be realized. Herein report our recent progress copper metallaphotoredox co‐catalyzed trifluoromethyl‐fluorosulfonylation alkenes with TFSP both CF 3 source. Valuable groups are added across double bonds. Besides, A wide array synthetically useful moieties featuring distinct electronic patterns various nitrogenous heterocycles well tolerated by strategy. magnified image

Language: Английский

Fluorosulfonyl radicals: new horizons for the synthesis of sulfonyl fluorides DOI
Fu‐Sheng He, Yuqing Li, Jie Wu

et al.

Organic Chemistry Frontiers, Journal Year: 2022, Volume and Issue: 9(19), P. 5299 - 5305

Published: Jan. 1, 2022

Recent advances in the generation of fluorosulfonyl radicals toward sulfonyl fluorides are highlighted.

Language: Английский

Citations

29
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
Recent advances in photochemical and electrochemical strategies for the synthesis of sulfonyl fluorides DOI
Yu Zheng, Wenguang Lu,

Tianting Ma

et al.

Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 11(1), P. 217 - 235

Published: Nov. 14, 2023

This review summarizes the latest achievements in photochemical and electrochemical strategies for synthesis of sulfonyl fluorides focuses on novel features proposed mechanisms.

Language: Английский

Citations

19
Fluorosulfonylvinylation of Unactivated C(sp3)–H via Electron Donor–Acceptor Photoactivation DOI

Xueyan Zhao,

Dengfeng Chen, Shengzhen Zhu

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(17), P. 3109 - 3113

Published: April 21, 2023

An electron donor-acceptor (EDA) complex photoactivation strategy for radical fluorosulfonylation is disclosed the first time. Simply upon blue light irradiation, FSO2 can be generated efficiently under catalyst-free, base-free, and additive-free conditions, which enables facile access to 6-keto alkenylsulfonyl fluorides from readily available propargyl alcohols FSO2Cl. The fluoride motif has been showcased as a versatile SuFEx hub with diverse follow-up derivatizations.

Language: Английский

Citations

18
FSO2 Radical-Initiated Tandem Addition Reaction of Two Different Olefins: A Facile Access to Multifunctional Aliphatic Sulfonyl Fluorides DOI

Na Yang,

Chenxi Mao,

Honghai Zhang

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(24), P. 4478 - 4482

Published: June 12, 2023

Multicomponent reactions represent a powerful method for building complex molecules from structurally simple starting materials. Herein, we report novel three-component radical–polar crossover reaction involving tandem addition of two different olefins, which is initiated by the selective fluorosulfonyl radicals to alkyl alkenes. This process provides facile and effective access multiple functionalized aliphatic sulfonyl fluoride molecules. Further transformation products also demonstrated.

Language: Английский

Citations

17
Electroreductive hydroxy fluorosulfonylation of alkenes DOI Creative Commons
Qingyuan Feng, Tianyu He, Shencheng Qian

et al.

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

Published: Dec. 13, 2023

An electroreductive strategy for radical hydroxyl fluorosulfonylation of alkenes with sulfuryl chlorofluoride and molecular oxygen from air is described. This mild protocol displays excellent functional group compatibility, broad scope, good scalability, providing convenient access to diverse β-hydroxy sulfonyl fluorides. These fluoride products can be further converted valuable aliphatic fluorides, β-keto β-alkenyl Further, some these showed inhibitory activity against Botrytis cinerea or Bursaphelenchus xylophilus, which could useful potent agrochemical discovery. Preliminary mechanistic studies indicate that this transformation achieved through rapid O2 interception by the alkyl subsequent reduction peroxy radical, outcompete other side reactions such as chlorine atom transfer, hydrogen Russell fragmentation.

Language: Английский

Citations

17
Radical Hydro-Fluorosulfonylation of Propargylic Alcohols via Electron Donor–Acceptor Photoactivation DOI

Yingyin Zhang,

Qingyuan Feng, Yu Zheng

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(7), P. 1410 - 1415

Published: Feb. 15, 2024

A radical hydro-fluorosulfonylation of propargyl alcohols with FSO2Cl is presented based on the photoactivation electron donor–acceptor (EDA) complex. The reaction avoids requirement for photocatalysts, bases, hydrogen donor reagents, any other additives, and harsh conditions, enabling facile synthesis various functionalized γ-hydroxy (E)-alkenylsulfonyl fluorides. These multifunctional sulfonyl fluorides can be further diversified, providing access to privileged molecules biological relevance.

Language: Английский

Citations

7
Aliphatic Sulfonyl Fluoride Synthesis via Decarboxylative Fluorosulfonylation of Hypervalent Iodine(III) Carboxylates DOI

Caiyun Ou,

Yinxia Cai,

Yuyang Ma

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(36), P. 6751 - 6756

Published: Sept. 1, 2023

We disclose herein a photocatalytic decarboxylative fluorosulfonylation reaction of various hypervalent iodine(III) carboxylates in combination with 1,4-diazabicyclo[2.2.2]octane–bis(sulfur dioxide) adduct as sulfonyl source and KHF2 desirable fluorine via radical sulfur dioxide insertion fluorination strategy. A one-pot carboxylic acids mediated by PhI(OAc)2 was realized, well. Notably, this transformation can be performed under heating conditions without the need for catalysts.

Language: Английский

Citations

15
Photocatalytic C–C Bond Cleavage and Fluorosulfonylation of Strained Cycloalkanols for Carbonyl-Containing Aliphatic Sulfonyl Fluorides DOI

Zhi-Min Yan,

Qi Lin,

Huijie Du

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(38), P. 7051 - 7056

Published: Sept. 20, 2023

In this report, we present a photocatalytic ring-opening fluorosulfonylation of strained cycloalkanols with sulfur dioxide and NFSI under mild conditions for the synthesis carbonyl-containing aliphatic sulfonyl fluorides. The synthetic potential fluoride products has been examined by diverse transformations, including SuFEx reactions Baeyer-Villiger oxidation reactions. Mechanistic studies demonstrate that reaction operates through radical C-C bond cleavage/SO2 insertion/fluorination cascade process.

Language: Английский

Citations

15
Aminofluorosulfonylation of β,γ-Unsaturated Hydrazones with Sulfur Dioxide and N-Fluorobenzenesulfonimide: Accessing Pyrazoline-Functionalized Aliphatic Sulfonyl Fluorides DOI

Zhi-Min Yan,

Qi Lin,

Tong-Yang Cao

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(21), P. 3910 - 3915

Published: May 24, 2023

An efficient aminofluorosulfonylation strategy was developed for the synthesis of various pyrazoline-functionalized aliphatic sulfonyl fluorides using β,γ-unsaturated hydrazones with sulfur dioxide and NFSI as starting materials under mild conditions. The fluoride products could be successfully transformed into corresponding sulfonate esters amides via sulfur(VI) exchange (SuFEx) click reactions. Preliminary mechanistic investigations demonstrate that reaction operates through a radical cyclization/SO2 insertion/fluorination cascade process.

Language: Английский

Citations

13