Metal‐Free Electrochemical Trifluoromethylation of Imidazole‐Fused Heterocycles with Trifluoromethyl Thianthrenium Triflate

Chinese Journal of Chemistry, Journal Year: 2024, Volume and Issue: 42(15), P. 1679 - 1685

Published: March 15, 2024

Comprehensive Summary A novel and eco‐friendly electrochemical activation of trifluoromethyl thianthrenium triflate (TT–CF 3 + OTf − ) for trifluoromethylation imidazole‐fused heteroaromatic compounds was established. This method involves the direct electrolysis TT–CF without requirement external oxidants or catalysts, aligning with principles green chemistry. wide range including imidazo[1,2‐ a ]pyridines benzo[ d ]imidazo[2,1‐ b ]thiazoles have been successfully trifluoromethylated using this technique, exhibiting excellent compatibility various functional groups broad substrate scope. Moreover, method's applicability one‐pot sequential reactions enables reduction waste resource consumption by eliminating need intermediate purification steps.

Language: Английский

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Fluorotrifluoromethylation of Alkenes Mediated by a Hypervalent Trifluoromethyl-Iodine(III) Reagent

Organic Letters, Journal Year: 2024, Volume and Issue: 26(19), P. 4158 - 4162

Published: May 2, 2024

Herein, we present a novel strategy for synthesizing polyfluorinated compounds by the fluorotrifluoromethylation of olefins, which was achieved through new trifluoromethyl-iodine(III) reagent TFNI-1. TFNI-1 readily synthesized via three-step process, and its structure characterized NMR spectroscopy X-ray crystallography. It is shown radical trapping clock experiments that reaction involves CF3 intermediate.

Language: Английский

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Electrochemical Strategy for the Radical Fluoroacetylation of Sulfoximines from Fluorinated Alkyl Carboxylic Acids

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: April 15, 2025

The integration of trifluoroacetyl (CF3CO) groups into organic skeletons is a key research topic in synthetic chemistry given their significant potential to boost biological activity. Despite recent developments strategies for incorporating moiety via radical intermediates, the practical utilization inexpensive and readily available trifluoroacetic acids as sources has not yet been developed. Herein, an electrochemical strategy employed achieve deoxygenative transformation directly with assistance PPh3. obtained radicals are then coupled sulfoximine species, thus enabling synthesis N-trifluoroacetylated sulfoximines. Additionally, other fluorinated alkyl carboxylic acids, including perfluoro-, difluoro-, trifluoromethylcarboxylic can also be efficiently utilized under these conditions, leading corresponding acylated Moreover, trifluoroacetylation drug-based molecules easy execution scale-up experiments highlight applicability this protocol.

Language: Английский

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Room Temperature Access to Bridged Nitrogen Ligands via Electroreductive Annulation of 1,10-Phenanthrolines and Imines

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: April 25, 2025

An electroreductive annulation reaction of 1,10-phenanthrolines and imines has been developed. This method proceeds with broad substrate functionality tolerance, high selectivity, no need for pressurized H2 gas or transition metal catalysts. Mechanistic studies reveal that the products are formed via simultaneous electroreduction both proton-activated reactants followed by radical cross-coupling intramolecular cyclization coupling adduct.

Language: Английский

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Electrochemical Decarboxylative Cross‐Coupling with Nucleophiles

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: unknown

Published: Aug. 19, 2024

Decarboxylative cross-coupling reactions are powerful tools for carbon-heteroatom bonds formation, but typically require pre-activated carboxylic acids as substrates or heteroelectrophiles functional groups. Herein, we present an electrochemical decarboxylative of with structurally diverse fluorine, alcohol, H

Language: Английский

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Molecular Electro(photo)catalysis: Triarylamine and Triarylimidazole Derivatives Mediated Oxidation Systems In Organic Electrosynthesis

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: 366(19), P. 3943 - 3962

Published: July 31, 2024

Abstract Organic electrosynthesis has become a green, efficient and sustainable alternative to traditional organic transformation for the redox reactions. In this connection, indirect electrolysis employing mediators is attaining increasing significance as it offers chance improve reaction selectivity avoids over‐oxidation/reduction issues encountered in direct electrolysis. Triarylamines triarylimidazoles, representative molecular mediators, have attracted widespread attention recent years due advantages of well‐defined easy structural modification tunable ability. Hence, minireview, growth triarylamine triarylimidazole derivatives mediated electrochemical oxidation reactions were presented, highlighting optimization, performance mechanism these mediators. Moreover, photocatalytic photoelectrocatalytic cases with also highlighted. To conclude, current challenges future prospects field are discussed.

Language: Английский

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Et₄NCl-Promoted Electrochemical Atherton-Todd Type Reaction to Construct P(O)–F Bonds

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(11), P. 7006 - 7014

Published: May 23, 2023

An electrochemical synthetic strategy to construct P(O)-F bonds was developed via the Atherton-Todd reaction. Promoted by Et4NCl, a series of biologically active phosphoric fluorides were synthesized use commercially available P(O)-H feedstocks and Et3N·3HF as F-source. With this protocol, some potentially functional P(O)-OR P(O)-SR motifs could also be smoothly forged. This sustainable fluorination approach features step-economy, is chemical-oxidant- metal-catalyst-free, offers low cost mild conditions. Additionally, cyclic voltammetry control experiments conducted propose reasonable mechanism.

Language: Английский

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Electrochemical Construction of C‐F Bonds: Recent Advances and Future Perspectives.

European Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 27(39)

Published: Aug. 9, 2024

Abstract Ideal pathways to synthesize fluorinated compounds were pursued for over 100 years, due wide application of organofluorides in materials, agrochemicals and pharmaceuticals. In this regard, electro‐organic synthesis, evolved as a sustainable scalable approach various synthetic protocols, stands out promising strategy. As result, many novel attracting applications introduction fluorine items into organic by direct redox‐mediated electrochemical methods has been reported, especially recent five years. review, we are aim highlight the reaction scopes, mechanism, fundamental aspects source variation electrochemcial fluoriation transformation.

Language: Английский

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Electrochemical trifluoroalkylation/annulation for the synthesis of CF₃-functionalized tetrahydroquinolines and dihydroquinolinones

Organic & Biomolecular Chemistry, Journal Year: 2023, Volume and Issue: 21(42), P. 8579 - 8583

Published: Jan. 1, 2023

Tuning the electronic structure of protecting groups on nitrogen atom substrates has emerged as an effective strategy to achieve tandem trifluoromethylation/C(sp2)-H annulation using Langlois' reagent CF3 source for electrochemical synthesis functionalized tetrahydroquinolines and dihydroquinolinones.

Language: Английский

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Electrochemically Direct Fluorination Functionalization of Styrenes with Different Fluorine Source: Access to Fluoroalkyl Derivatives

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(13), P. 9440 - 9449

Published: June 14, 2024

A mild protocol for electrochemically oxidative fluorodifunctionalization of styrenes has been demonstrated. The reaction proceeds under metal, external oxidant, and catalyst free conditions, allowing tunable access to a wide variety synthetically useful fluoroalkyl derivatives, such as β-fluorosulfone/fluoromethyl, fluorothiocyanation, vinylsulfonyl derivatives. Moreover, CsF was shown be the proper fluorine source this electrochemical transformation.

Language: Английский

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