Visible Light‐Driven Metal‐ and Photocatalyst‐Free Synthesis of β‐Trifluoromethylated Enamines via Trifluoromethyl Thianthrenium Salts DOI Open Access
Liang Jiang,

Yisong Tang,

S.S. Li

et al.

Chemistry - An Asian Journal, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 29, 2024

A novel protocol for the visible-light-driven synthesis of β-trifluoromethylated enamines has been developed, which operates without use transition metals or any photocatalysts, utilizing trifluoromethylthiosulfonium salts as source trifluoromethyl groups under mild conditions. According to this new protocol, more than 40 products have prepared in moderate good yields. In addition eliminating need expensive toxic and methodology proves its potential scalability through air-stability, safe readily available reagents, a two-step one-pot procedure, effective gram-scale reactions. This innovative approach not only demonstrates promise green chemical but also offers pathway advancement fluorine chemistry sustainable organic synthesis.

Language: Английский

Oxidative Substitution of Organocopper(II) by a Carbon-Centered Radical DOI

Yuecheng Weng,

Yuxuan Jin,

Jian Wu

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(33), P. 23555 - 23565

Published: Aug. 8, 2024

Copper-catalyzed coupling reactions of alkyl halides are believed to prominently involve copper(II) species and radicals as pivotal intermediates, with their exact interaction mechanism being the subject considerable debate. In this study, a visible light-responsive fluoroalkylcopper(III) complex, [(terpy)Cu(CF3)2(CH2CO2tBu)] Trans-1, was designed explore mechanism. Upon exposure blue LED irradiation, Trans-1 undergoes copper–carbon bond homolysis, generating Cu(II) carbon-centered radicals, where radical then recombines intermediate, resulting in formation Cis-1, Cis isomer Trans-1. Beyond this, well-defined fluoroalkylcopper(II) intermediate ligated sterically hindered ligand isolated underwent full characterization electronic structure studies. The collective experimental, computational, spectroscopic findings work strongly suggest that organocopper(II) engages via an "oxidative substitution" mechanism, which is likely operational pathway for copper-catalyzed C–H trifluoromethylation reactions.

Language: Английский

Citations

9
Visible Light-Induced Radical Cascade Difluoromethylation/Cyclization of Unactivated Alkenes: Access to CF2H-Substituted Polycyclic Imidazoles DOI Creative Commons
S.J. Lin, Yuanyuan Deng,

Hanxun Zhong

et al.

ACS Omega, Journal Year: 2024, Volume and Issue: 9(26), P. 28129 - 28143

Published: June 19, 2024

An efficient and mild protocol for the visible light-induced radical cascade difluoromethylation/cyclization of imidazoles with unactivated alkenes using easily accessible bench-stable difluoromethyltriphenylphosphonium bromide as precursor -CF

Language: Английский

Citations

5
Acylmonofluoromethylation of alkenes via dual NHC/photoredox catalysis DOI
Shichao Tian, Mingxi Chen, Yihan Tang

et al.

Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 10(24), P. 6124 - 6130

Published: Jan. 1, 2023

We herein describe a three-component radical acylmonofluoromethylation of alkenes by cooperative NHC/photoredox catalysis to synthesize various monofluorinated alkyl aryl ketones.

Language: Английский

Citations

11
Radical Acylfluoroalkylation of 1,3-Enynes via N-Heterocyclic Carbene/Photoredox Cooperative Catalysis DOI
Shichao Tian, Ning Chen, Keguang Cheng

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(20), P. 4351 - 4355

Published: May 10, 2024

We report a novel three-component radical acylfluoroalkylation of 1,3-enynes by synergistic N-heterocyclic carbene (NHC)/photoredox catalysis toward various fluorinated allenic aryl ketones. This protocol features broad substrate scope and excellent functional group tolerability, with examples late-stage modification drug molecules natural products. Notably, seven different fluoroalkyl motifs can be introduced to 1,3-enynes, further demonstrating the robustness generality this method. The generation from each sulfinate reagent was individually supported EPR experiments.

Language: Английский

Citations

4
Catalyst‐Free, Radical Tri‐ and Difluoromethylation of Isocyanides and N‐Arylacrylamides Using Rotating Magnetic Field and Metal Rods DOI Open Access

Xuliang Han,

Haodong Liu,

Xiaomei Feng

et al.

Chinese Journal of Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 7, 2024

Comprehensive Summary The pursuit of sustainable and environmentally benign synthetic methods continues to challenge organic chemists. Herein, we introduce a magnetoredox system for tri‐ difluoromethylation isocyanides N ‐arylacrylamides using rotating magnetic field steel rods. This approach enables facile synthesis functionalized phenanthridines oxindoles without the need catalysts additives under mild conditions. Such potentially represents an attractive strategy selective formation bonds through multifaceted regulation intensity, frequency, rod size.

Language: Английский

Citations

4
Discovery of a Distinctive Reagent for Divergent Arene Trifluoromethylsulfinylation DOI Creative Commons
Liuqing Yang, Yu Lu, Lulu Liu

et al.

JACS Au, Journal Year: 2025, Volume and Issue: 5(3), P. 1448 - 1459

Published: Feb. 19, 2025

Simple and direct arene trifluoromethylsulfinylation is highly desirable in drug design but remains a major challenge. Herein, we report modular, mild, innate C–H of wide variety arenes via distinctive trifluoromethylsulfinylating reagent N-hydroxyphthalimide-O-trifluoromethanesulfinate following divergent efficient pathways. This can be conducted redox-neutral manner at room temperature with light-, metal-, photocatalyst-free mild conditions. Mechanistic studies density functional theory (DFT) calculations revealed that the success this approach hinges upon an activated trifluoromethanesulfite ester proceeds homolytic cleavage very low bond dissociation energy to generate dummy aminoxyl radical (PINO) active CF3S(O) radical, which could accidentally transformed into trifluoromethanesulfonic anhydride, CF3S(O)OS(O)CF3, for transfer S(O)CF3 group exemplary set strong EDG-substituted arenes. DFT computation corroborates novel by TfOH heterolytic produce CF3S(O)OTf, responsible electrophilic challenging weak substrates through addition–elimination mechanism. Such functionalization using affords innovative strategy marked improvement over previously developed reagents. Notably, simple conditions, broad reactivities, good compatibility, reaction modes (homolysis heterolysis), as well late-stage (LST) complex biologically molecules these reactions underline great potential preparation functionalized drug-like molecules.

Language: Английский

Citations

0
Electrochemical Access to Difluoromethyl Groups: An Overview of Scope, Mechanisms, and Challenges DOI
Seonyoung Kim, Hyunwoo Kim

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 6826 - 6851

Published: April 14, 2025

Language: Английский

Citations

0
Visible-Light-Driven Tandem Cyclization of o-Hydroxyaryl Enaminones: Access to 3-(α-Arylsulfonamido)trifluoroethyl Chromones DOI
Jinwei Yuan, Qiang Liu,

X. H. Liu

et al.

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: April 22, 2025

A visible-light-driven intermolecular tandem α-amidotrifluoroethylation/cyclization of enaminones using a previously unreported N-trifluoroethylaminopyridinium salt was achieved in the absence transition metal catalysts or bases. Notable features this synthetic method include mild conditions, high selectivity, excellent functional group compatibility, and satisfactory yields. Preliminary mechanistic studies indicate that reaction proceeds via radical pathway, involving an situ generated N-trifluoroethyl radical, followed by 1,2-H shift.

Language: Английский

Citations

0
Photo-induced decarboxylative radical cascade cyclization of unactivated alkenes: access to CF- and CF2-substituted ring-fused imidazoles DOI Creative Commons
Hui-Nan Wang, Shaohui Lin, Hui Hong

et al.

RSC Advances, Journal Year: 2025, Volume and Issue: 15(16), P. 12739 - 12745

Published: Jan. 1, 2025

A mild and effective visible-light-induced decarboxylative radical cascade reaction of olefin-containing imidazoles α-fluorinated carboxylic acids, has been developed to afford monofluoromethylated or aryldifluoromethylated polycyclic imidazoles.

Language: Английский

Citations

0
Photoredox-catalyzed direct C–H monofluoromethylation of heteroarenes DOI
Nagarajan Ramkumar,

Ketrina Plantus,

Melita Ozola

et al.

New Journal of Chemistry, Journal Year: 2023, Volume and Issue: 47(44), P. 20642 - 20652

Published: Jan. 1, 2023

We report a photo-redox catalyzed radical C–H monofluoromethylation of heterocycles, thus demonstrating this process and the importance monofluoromethyl unit in medicinal drug discovery purposes.

Language: Английский

Citations

6