Catalyst‐Free Defluoroalkylation of Trifluoromethylated Alkenes via Photoinduced Electron Donor‐Acceptor Complex DOI
Pan Gao,

Zhang Qing-zheng,

Yicheng Li

et al.

ChemistrySelect, Journal Year: 2023, Volume and Issue: 8(22)

Published: June 6, 2023

Abstract Radicals can be formed expeditiously through the direct irradiation of an electron donor‐acceptor (EDA) complex. Herein, we show a photocatalyst‐free strategy for gem ‐difluoroalkenes synthesis realized by photo‐irradiation EDA complexes, which generated in situ between N ‐alkylpyridinium salts and Hantzsch ester without any other additives. A wide variety readily available alkylamines underwent deaminative defluoroalkylation to provide corresponding ‐difluoroalkenes. This reaction system exhibits high reactivity good functional group tolerance provides practical effective entry broad range α ‐alkyl‐substituted

Language: Английский

Metal-free, visible-light driven α-C(sp3)–H gem-difluoroallylation of glycine derivatives with trifluoromethyl alkenes and 1,3-enynes DOI

Zi-Hang Yuan,

Xin Hong, Lu Zhang

et al.

Green Chemistry, Journal Year: 2023, Volume and Issue: 25(17), P. 6733 - 6738

Published: Jan. 1, 2023

A metal free, visible-light driven α-C(sp 3 )−H gem-difluoroallylation of glycine derivatives with CF -alkenes and 1,3-enynes is presented under redox-neutral conditions good yields excellent functional group compatibility.

Language: Английский

Citations

28
Direct Hydrodefluorination of CF3-Alkenes via a Mild SN2′ Process Using Rongalite as a Masked Proton Reagent DOI
Xiang‐Long Chen, Dongsheng Yang, Bo‐Cheng Tang

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(13), P. 2294 - 2299

Published: March 23, 2023

A concise and efficient hydrodefluorination process was developed for the synthesis of gem-difluoroalkenes. This reaction employs rongalite as a masked proton source does not require any additional catalysts or reductants. Notably, trifluoromethyl alkenes having both terminal internal double bonds are compatible with this process, allowing wider range substrates. The successful late-stage functionalizations pharmaceuticals gram-scale syntheses were used to demonstrate viability method.

Language: Английский

Citations

27
Photo/Ni dual-catalyzed radical defluorinative sulfonylation to synthesizegem-difluoro allylsulfones DOI Open Access

Yiran Xu,

Shengchun Wang, Zhao Liu

et al.

Chemical Communications, Journal Year: 2023, Volume and Issue: 59(25), P. 3707 - 3710

Published: Jan. 1, 2023

Radical defluorinative functionalization of α-trifluoromethyl styrenes represents an effective way toward gem-difluoroalkenes. There are general interests in developing novel synthetic protocols for with various types radicals. However, reports on the preparation gem-difluoro allylsulfones via S-centered radical pathway limited. Herein, we developed a photo/nickel dual-catalyzed sulfonylation that rapidly and reliably synthesizes allylsulfones. The merit this protocol is exhibited by its mild conditions wide scope, thus providing strategy sulfonyl participating coupling.

Language: Английский

Citations

17
Visible light-promoted defluorinative alkylation/arylation of α-trifluoromethyl alkenes with thianthrenium salts DOI
Yue Zhang, Jianyou Mao, Zhihong Wang

et al.

Green Chemistry, Journal Year: 2024, Volume and Issue: 26(17), P. 9371 - 9377

Published: Jan. 1, 2024

Defluorinative alkylation and arylation between thianthrenium salts α-trifluoromethyl alkene to afford gem -difluoroolefins by easily recycling thianthrene under visible light irradiation free of metal photocatalyst.

Language: Английский

Citations

8
Gem-Difluoroallylation of Aryl Sulfonium Salts DOI
Yue Zhao, Claire Empel,

Wenjing Liang

et al.

Organic Letters, Journal Year: 2022, Volume and Issue: 24(48), P. 8753 - 8758

Published: Nov. 28, 2022

The unprecedented photochemical late-stage defluorinative gem-difluoroallylation of aryl sulfonium salts, which are formed site-selectively by direct C(sp2)─H functionalization, is herein disclosed. This method distinguished its mild reaction conditions, wide scope, and excellent site-selectivity. As showcase examples, a Flurbiprofen Pyriproxyfen derivatives could be late stage gem-difluoroallylated with high yields. Experimental computational investigations were conducted.

Language: Английский

Citations

25
Visible-light-mediated C–F bond cleavage for the synthesis of polyfluorinated compounds DOI
Bin Wang,

Cui‐Tian Wang,

Xuesong Li

et al.

Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 10(13), P. 3341 - 3346

Published: Jan. 1, 2023

Herein, we describe a novel and efficient photo-redox catalytic difluorinated ester radical addition/defluoroalkylation coupling reaction between trifluoroacetic acid derivatives α-trifluoromethyl alkenes.

Language: Английский

Citations

11
Transition‐Metal‐Free Allylic Defluorination Cross‐Electrophile Coupling Employing Rongalite DOI
Xiang‐Long Chen, Chun‐Yan Wu, Dong‐Sheng Yang

et al.

Chinese Journal of Chemistry, Journal Year: 2024, Volume and Issue: 42(12), P. 1360 - 1366

Published: Feb. 23, 2024

Comprehensive Summary The conversion of CF 3 ‐alkenes to gem ‐difluoroalkenes using reductive cross‐coupling strategy has received much attention in recent years, however, the use green and readily available reducing salt mediate these reactions remains be explored. In this work, a concise construction gem‐ difluoroalkenes, which requires neither catalyst nor metal agent, was established. Rongalite, safe inexpensive industrial product, employed as both radical initiator reductant. This procedure compatible with linear cyclic diaryliodonium salts, enabling wide variety substrates (>70 examples). utility approach demonstrated through gram‐scale synthesis efficient late‐stage functionalizations anti‐inflammatory drugs.

Language: Английский

Citations

4
New Opportunities to Access Fluorinated Molecules Using Organophotoredox Catalysis via C(sp3)–F Bond Cleavage DOI Creative Commons
Sourav Roy, Tatiana Besset

JACS Au, Journal Year: 2025, Volume and Issue: 5(2), P. 466 - 485

Published: Feb. 7, 2025

Fluorinated molecules are of paramount importance because their unique properties. As a result, the search for innovative approaches to synthesis this class compounds has been relentless over years. Among these, combination photocatalysis and organofluorine chemistry turned out be an effective partnership access unattainable fluorinated molecules. This Perspective provides overview recent advances in synthesizing via organophotoredox-catalyzed defluorination process from trifluoromethylated compounds. It encompasses preparation difluoromethylated (hetero)arenes, amides, esters as well gem-difluoroalkene derivatives using C(sp3)–F bond activation or β-fragmentation. will highlight remaining challenges discuss future research opportunities.

Language: Английский

Citations

0
Visible-Light-Mediated Radical α-C(sp3)─H gem-Difluoroallylation of Amides with Trifluoromethyl Alkenes via Halogen Atom Transfer and 1,5-Hydrogen Atom Transfer DOI
Dan Liu,

Fang Xiao,

Ben Ebel

et al.

Organic Letters, Journal Year: 2025, Volume and Issue: 27(10), P. 2377 - 2382

Published: March 5, 2025

Direct gem-difluoroallylation at the α-carbonyl position is a challenging process by conventional methods. Herein we report photocatalytic radical α-C(sp3)─H of amides with trifluoromethyl alkenes to access target compounds good yields and functional group tolerance. The mild effective conditions allow gem-difluoroalkene motifs as carbonyl bioisosteres incorporated concisely some complex molecules, including gemfibrozil estrone derivatives, presenting great potential for late-stage functionalization drugs, natural products, bioactive intermediates. Mechanistic investigations suggest pathway combining XAT 1,5-HAT.

Language: Английский

Citations

0
N‐Directed defluorinative γ‐C(sp3)−H allylation of sulfamate esters for synthesis of gem‐difluoroalkenes via photoredox catalysis DOI
Jiawen Yang, Meng Li,

Guang‐Qiang Tan

et al.

European Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 27(17)

Published: March 29, 2024

Abstract gem ‐Difluoroalkenes are unique structural motifs with important applications ranging from drugs to materials. Herein, we report a novel radical‐mediated defluorinative allylation of sulfamate esters through distal C(sp 3 )−H functionalization under photoredox conditions. The reaction could readily incorporate various ‐difluoroalkene into previously unfunctionalized sp carbon centers. transformation allows directly dual activation N−H and bonds via photocatalytic redox‐neutral process, as well using water environmentally friendly co‐solvent. provide general operationally simple method access compounds high diversity.

Language: Английский

Citations

2