An in-situ Generated Proton Initiated Aromatic Fluoroalkylation via Electron Donor-Acceptor Complexes Photoactivation

Green Chemistry, Journal Year: 2024, Volume and Issue: 26(12), P. 7198 - 7205

Published: Jan. 1, 2024

In situ -generated protonated aromatic hydrocarbons overcome their intrinsic electronic properties to serve as catalytic electron acceptors, avoiding the use of photocatalysts, metals, and redox reagents achieve fluoroalkylation.

Language: Английский

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para-Selective C–H alkylation of aroyl chlorides through organic photoredox-catalyzed radical tele-substitution

Chem, Journal Year: 2025, Volume and Issue: unknown, P. 102446 - 102446

Published: Feb. 1, 2025

Language: Английский

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Direct Perfluoroalkylation of C−H Bonds in (Hetero)arenes

Chemistry - A European Journal, Journal Year: 2022, Volume and Issue: 28(41)

Published: May 11, 2022

Abstract Perfluoroalkylated (hetero)arenes represent an extremely important family of molecules commonly utilized in many areas such as medicinal chemistry, agrochemistry and material sciences. Due to their unique properties, they have attracted significant interest from synthetic chemists various methods been developed for synthesis. Among them, the direct perfluoroalkylation C(sp 2 )−H bonds is one most attractive straightforward ones, provided that it proceeds with high levels regioselectivity. In this review article, a comprehensive overview advances field presented, special focus on reaction mechanisms involved these transformations All available classified according nature perfluoroalkyl chain introduced, trifluoromethylation reactions being overviewed separate section, reagents/catalysts required.

Language: Английский

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Synthesis of Trifluoromethyl-Substituted Allenols via Catalytic Trifluoromethylbenzoxylation of 1,3-Enynes

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(3), P. 2142 - 2148

Published: Jan. 25, 2023

Allenol has been identified as a versatile building block for organic synthesis, and numerous efforts have made to synthesize apply allenol. However, limited obtain trifluoromethyl-substituted Here, by using readily available 1,3-enyne the starting material, copper-catalyzed trifluoromethylbenzoxylation process was developed efficient synthesis of allenols Togni-II reagent reaction partner. Triple roles reagent, including source trifluoromethyl group, hydroxyl oxidant, were elucidated in this transformation. Moreover, late-stage diversification performed, which revealed application potential preparation various compounds.

Language: Английский

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para‐Selective Radical Trifluoromethylation of Benzamide Derivatives via Iminium Intermediates

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(36)

Published: June 23, 2022

The direct C-H trifluoromethylation of arenes via a radical pathway has attracted considerable attention recently. However, major challenge is the lack site-selectivity on phenyl ring especially para-selectivity. Herein we show new strategy for para-selective benzamide derivatives using iminium activation. reaction undergoes radical-type nucleophilic substitution instead electrophilic owing to activation as result lowering LUMO (lowest unoccupied molecular orbital). A wide range substrates are compatible with this method giving almost exclusive para-trifluoromethylated products.

Language: Английский

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Visible-Light-Mediated Ruthenium-Catalyzed para-Selective Alkylation of Unprotected Anilines

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(11), P. 7310 - 7321

Published: May 15, 2023

Anilines are important moieties in organic chemistry, pharmaceuticals, and materials science. Although para-selective functionalization of anilides tertiary anilines is well established, unprotected have posed a challenge. Herein, we report visible-light-mediated Ru(II)-catalyzed para-alkylation anilines. The distinct Ru(II)–aniline complex enabled the reaction to proceed with extremely high efficiency (2 h) under mild conditions. good functional group tolerance allowed late-stage even aggregation-induced emission luminogen labeling natural products drugs. A mechanistic investigation suggests that crucial for both triggering controlling para-selectivity.

Language: Английский

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A radical approach towards polarity-reversed para-substitution of electron-deficient arenes

Chemical Communications, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

We have developed a protocol for polarity-reversed para-substitution of electron-deficient arenes. In order to achieve desired reactivity and selectivity broad range substrates, the dual pronged strategy is essential. Furthermore, this approach has also shown promise in perfluoroalkylation Control experiments computational studies provide mechanistic insight observed selectivity. The potential drug design synthesis been showcased by economical ecofriendly method that provides access variety building blocks.

Language: Английский

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Advances in photocatalytic research on decarboxylative trifluoromethylation of trifluoroacetic acid and derivatives

Frontiers in Chemistry, Journal Year: 2025, Volume and Issue: 13

Published: May 14, 2025

Trifluoromethylation stands as a pivotal technology in modern synthetic chemistry, playing an indispensable role drug design, functional material development, and agrochemical innovation. With the growing emphasis on green chemistry principles, pursuit of environmentally benign trifluoromethylation strategies has emerged critical research frontier. Trifluoroacetic acid (TFA), characterized by its cost-effectiveness, stability, low toxicity, become promising alternative to conventional reagents. This review systematically summarizes advancements photocatalytic decarboxylative using TFA derivatives over past decade, focusing three key activation mechanisms: single-electron transfer (SET), electron donor-acceptor (EDA) complex-mediated pathways, ligand-to-metal charge (LMCT). paradigm shift is driven intrinsic limitations thermal decarboxylation, particularly reliance harsh conditions significant environmental burdens. In contrast, enable efficient C–CF 3 bond construction under mild conditions, offering modular platform for synthesizing fluorinated molecules. Strategic priorities should focus overcoming fundamental challenges, including but not limited optimizing photosensitizer catalytic efficiency, establishing regioselective manipulation strategies, engineering multicomponent tandem reaction systems achieve methodologies conditions. Furthermore, integration mechanistic investigations with artificial intelligence-driven prediction will accelerate advancement precision technologies. progress anticipated provide sustainable solutions next-generation pharmaceuticals advanced materials, effectively bridging innovation gap between academic industrial implementation.

Language: Английский

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Visible-Light Photoredox Catalysis for the Synthesis of Fluorinated Aromatic Compounds

Catalysts, Journal Year: 2023, Volume and Issue: 13(1), P. 94 - 94

Published: Jan. 2, 2023

Fluorine-containing functional groups are important motifs influencing physical and biological properties of organic compounds. Visible-light photoredox catalysis as a powerful strategy for the activation small molecules contributed significantly to rapid progress new synthetic procedures allowing introduction fluorine atoms into substrates. In this review, we highlight distinct strategies transition metal- organic-photocatalytic fluorination arenes heteroarenes by broad range fluorinating The presented divided two groups. first group involves reactions enabling direct attachment CF3-, CnFm-, F-, CF3O-, CF3S-, SO2F- substituents various aromatic second presents tandem where formation system occurs after installation fluorine-containing on non-aromatic fragment molecule.

Language: Английский

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Palladium‐Catalyzed Asymmetric Trifluoromethylated Allylic Alkylation of N‐Substituted Glycine Ethyl Esters with α‐(Trifluoromethyl)alkenyl Acetates

European Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 26(36)

Published: July 19, 2023

Abstract An efficient strategy for asymmetric trifluoromethylated allylic alkylation of easily available N ‐substituted glycine ethyl esters with α ‐(trifluoromethyl)alkenyl acetates has been developed. Catalyzed by a [Pd(C 3 H 5 )Cl] 2 /( R )‐BINAP, various trifluoromethyl‐containing ester derivatives are afforded good yields and excellent enantioselectivities. The product can be readily converted into diverse fluoro‐substituted species, which shows the practicability this method.

Language: Английский

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