Photoredox-catalyzed stereo- and regioselective vicinal fluorosulfonyl-borylation of unsaturated hydrocarbons DOI Creative Commons

Heyin Li,

Mengjun Huang,

Zhenlei Zou

et al.

Chemical Science, Journal Year: 2023, Volume and Issue: 14(47), P. 13893 - 13901

Published: Jan. 1, 2023

There has been considerable research on sulfur(vi) fluoride exchange (SuFEx) chemistry, which is considered to be a next-generation click reaction, and relies the unique balance between reactivity stability inherent in high valent organosulfur. The synthetic versatility of bifunctional handles containing fluorosulfonyl group presents great value opportunity for drug discovery. However, direct photoredox-catalyzed fluorosulfonyl-borylation process remains unexplored challenging due its system incompatibility limited strategies. Herein, we developed sequential photocatalytic radical difunctionalization strategy highly efficient stereoselective synthesis vicinal borides (VFSBs) with an integrated redox-active SO2F reagent. VFSBs acted as orthogonal synthons, were subjected range convenient transformations via cleavage C-B S(vi)-F bonds, including halogenation, Suzuki coupling, hydrogenation, SuFEX demonstrated potential VFSB moieties use skeleton linkage modification.

Language: Английский

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

21
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
Synthetic strategies for fluorosulfonylated compounds: application to click chemistry reactions DOI
Sebastián Barata‐Vallejo, Damian E. Yerien, Al Postigo

et al.

Catalysis Science & Technology, Journal Year: 2023, Volume and Issue: 13(9), P. 2597 - 2617

Published: Jan. 1, 2023

Fluorosulfonylation of (hetero)aromatic and aliphatic compounds with emphasis on the use fluorosulfonylating hubs is discussed. Examples click chemistry (SuFEx) reactions diversity oriented clicking (DOC) processes are provided.

Language: Английский

Citations

18
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
Electrochemical Multicomponent Synthesis of Alkyl Alkenesulfonates using Styrenes, SO2 and Alcohols DOI Creative Commons
Aloisio de Andrade Bartolomeu,

Florian A. Breitschaft,

Dieter Schollmeyer

et al.

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: 30(21)

Published: Feb. 9, 2024

Abstract A novel electrochemical approach to access alkyl alkenesulfonates via a multicomponent reaction was developed. The metal‐free method features easy‐to‐use SO 2 stock solution forming monoalkylsulfites from alcohols with an auxiliary base in‐situ. These intermediates serve dual role as starting materials and supporting electrolyte enabling conductivity. Anodic oxidation of the substrate styrene, radical addition these consecutive second deprotonation preserve double bond form β‐styrenesulfonates in highly regio‐ stereoselective fashion. feasibility this electrosynthetic is demonstrated 44 examples yields up 81 %, employing various styrenes related substrates well diverse set alcohols. gram‐scale experiment underlines applicability process, which uses inexpensive readily available electrode materials.

Language: Английский

Citations

7
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
Hydrosulfonylation of Unactivated Alkenes and Alkynes by Halogen-Atom Transfer (XAT) Cleavage of SVI–F Bond DOI
Wu Xing, Bing Gao

Organic Letters, Journal Year: 2023, Volume and Issue: 25(48), P. 8722 - 8726

Published: Nov. 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.

Language: Английский

Citations

16
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