Synfacts, Journal Year: 2023, Volume and Issue: 19(12), P. 1253 - 1253
Published: Nov. 15, 2023
Key words fluorination - azaarenes C–H functionalization electron-transfer
Language: Английский
Chem, Journal Year: 2023, Volume and Issue: 10(2), P. 628 - 643
Published: Nov. 21, 2023
Language: Английский
Citations
22
Accounts of Chemical Research, Journal Year: 2024, Volume and Issue: 57(21), P. 3161 - 3181
Published: Sept. 20, 2024
ConspectusLate-stage halogenation, targeting specific positions in complex substrates, has gained significant attention due to its potential for diversifying and functionalizing molecules such as natural products pharmaceutical intermediates. Utilizing readily available halogenating reagents, hydrogen halides (HX), N-halosuccinimides (NXS), dichloroethane (DCE) reagents late-stage halogenation shows great promise expanding the toolbox of synthetic chemists. However, reactivity haleniums (X
Language: Английский
Citations
7
Chinese Journal of Chemistry, Journal Year: 2024, Volume and Issue: 42(10), P. 1128 - 1132
Published: Feb. 6, 2024
Comprehensive Summary A mild and practical method for synthesizing fluorinated quinoline derivatives, which have a wide range of applications in pharmaceuticals, materials, organic synthesis, was described through C—F bond insertion into indoles using CHBr 2 F. The simple conditions, readily availability F, as well the versatility transformations make this strategy very powerful 3‐fluoroquinoline 3‐fluoroquinolone. mechanistic studies reveal that bromofluorocarbene generated in‐situ under basic condition key intermediate.
Language: Английский
Citations
5
Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(45), P. 30758 - 30763
Published: Nov. 1, 2024
Organofluorine compounds, including fluorinated pyridines and isoquinolines, play a crucial role in pharmaceuticals, agrochemicals, materials science. However, step-economic selective C-H-functionalization to access these azaarenes is still underexplored, with
Language: Английский
Citations
5
Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)
Published: Aug. 28, 2024
Regioselective C-H functionalization of pyridines remains a persistent challenge due to their inherent electronically deficient properties. In this report, we present strategy for the selective pyridine C3-H thiolation, selenylation, and fluorination under mild conditions via classic N-2,4-dinitrophenyl Zincke imine intermediates. Radical inhibition trapping experiments, as well DFT theoretical calculations, indicated that thiolation selenylation proceeds through radical addition-elimination pathway, whereas two-electron electrophilic substitution pathway. The pre-installed electron-deficient activating N-DNP group plays crucial positive role, with additional benefit recyclability. practicability protocol was demonstrated in gram-scale synthesis late-stage modification pharmaceutically relevant pyridines.
Language: Английский
Citations
4
Angewandte Chemie International Edition, Journal Year: 2025, Volume and Issue: unknown
Published: Jan. 28, 2025
Abstract The iodination of electron‐deficient arenes and heteroarenes is a long‐standing problem in organic synthesis. Herein we describe the electrochemical nitromethane with Bu 4 NI as iodine source supporting electrolyte under Lewis acid‐free conditions presence small amounts chloride anions. electrochemically generated reagent could be applied for halogenated arenes, aromatic aldehydes, acids, esters, ketones, well nitroarenes to afford products good excellent yields.
Language: Английский
Citations
0
Angewandte Chemie, Journal Year: 2025, Volume and Issue: unknown
Published: Jan. 28, 2025
Abstract Die direkte Iodierung von elektronenarmen Aromaten und Heteroaromaten ist ein seit langer Zeit ungelöstes Problem in der Organischen Synthese. In diesem Beitrag beschreiben wir die elektrochemische Nitromethan mit Bu 4 NI als Iodid‐Quelle Leitsalz unter Lewis‐Säure freien Bedingungen Anwesenheit katalytischen Mengen Chlorid‐Ionen. Das elektrochemisch generierte Reagenz konnte für halogenierten Aromaten, aromatischen Aldehyden, Säuren, Estern, Ketonen sowie Nitroaromaten genutzt werden, um gewünschten Produkte guten bis exzellenten Ausbeuten zu erzeugen.
Citations
0
Accounts of Chemical Research, Journal Year: 2025, Volume and Issue: unknown
Published: Feb. 27, 2025
ConspectusPyridine is a crucial heterocyclic compound in organic chemistry. Typically, the pyridine motif behaves as an N-nucleophile and electron-deficient aromatic ring. Transforming ring into electron-rich system that exhibits reactivity contrary to classical expectations could unveil new opportunities This Account describes approach umpolung of through formation unprecedented N-boryl pyridyl anion (N-BPA) intermediate enables catalysis transformations.In 2017, we discovered 4-phenylpyridine acts efficient catalyst for borylation iodo- bromoarenes using diboron(4) compounds. Mechanistic studies revealed situ N-BPA pyridine/diboron(4)/methoxide reaction pivotal step this transformation. Further investigations showed dual reactivities both strong electron donor potent nucleophile. unique profile has unveiled novel pathways redox catalysis, derivatizations, transformations.Based on electron-donor characteristic anion, have developed catalytic mediated by catalyst. In pyridine/diboron(4)/base system, followed single transfer (SET) substrate with regeneration molecule establishes cycle. single-electron reduction variety substrates employing source. Upon visible-light excitation, transitions its excited state, exhibiting significantly enhanced reductivity. establishment modular photoredox consisting various combinations allow fine-tuning property. Using strategy, performed series challenging reactions, including -electron nonactivated chloro- fluoroarenes, Birch arenes.The nucleophilic character was effectively harnessed facilitate derivatization transformations. By directly quenching situ-generated proton source, practical N-H-1,4-dihydropyridines (DHPs). Bimolecular substitution between alkyl bromide produced 4-alkyl-1,4-DHP, which subsequently releases radical under conditions. process enabled transformation bromides radicals. Employing 4-trifluoromethylpyridine chemistry, resulting undergoes elimination fluoride yield 4-pyridyldifluoromethyl nucleophile, then reacts electrophiles realize defluorinative functionalization forge pyridyldifluoromethyl Alternatively, when 4-perfluoroalkylthiopyridine employed, similar occurred form perfluoroalkyl demonstrating perfluoroalkylation reagent offers distinct advantages over traditional reagents.The described provide insights We anticipate these findings will inspire further exploration mechanisms related
Language: Английский
Citations
0
Organic Letters, Journal Year: 2025, Volume and Issue: unknown
Published: April 14, 2025
In this study, we developed a photoredox-catalyzed defluorinative cross-coupling method for trifluoroketones and alkyl boronic acids. The reaction afforded series of novel α,α-difluoroketone derivatives, in vitro fungicidal activity revealed that some these compounds exhibited moderate to excellent against Rhizoctonia solani Botrytis cinerea. particular, compound 3d showed an EC50 value 4.27 μg/mL B. cinerea can be used as lead further optimization.
Language: Английский
Citations
0
Chemical Reviews, Journal Year: 2025, Volume and Issue: unknown
Published: April 22, 2025
Fluorine and nitrogen form a successful partnership in organic synthesis, medicinal chemistry, material sciences. Although fluorine-nitrogen chemistry has long rich history, this field received increasing interest made remarkable progress over the past two decades, driven by recent advancements transition metal organocatalysis photochemistry. This review, emphasizing contributions from 2015 to 2023, aims update state of art synthesis applications nitrogen-based organofluorine functional molecules chemistry. In dedicated sections, we first focus on fluorine-containing reagents organized according type groups attached nitrogen, including N-F, N-RF, N-SRF, N-ORF. review also covers nitrogen-linked building blocks, catalysts, pharmaceuticals, agrochemicals, underlining these components' broad applicability growing importance modern
Language: Английский
Citations
0