Monodefluorinative Halogenation of Perfluoroalkyl Ketones via Organophosphorus-Mediated Selective C–F Activation

JACS Au, Год журнала: 2025, Номер unknown

Опубликована: Янв. 28, 2025

Through the prosperity of organofluorine chemistry in modern organic synthesis, perfluorinated compounds are now abundant and widely available. Consequently, these substances become attractive starting materials for production complex, multifunctional fluorinated molecules. However, inherent challenges associated with activation discrimination C–F bonds typically lead to overdefluorination as well functional group incompatibility. To address problems, our utilized a rationally designed organophosphorus reagent that promoted mild selective manipulation single bond trifluoromethyl pentafluoroethyl ketones via an interrupted Perkow-type reaction, which allowed replacement fluorine more labile synthetically versatile congeners such chlorine, bromine, iodine. The resulting α-haloperfluoroketones have two reactive units orthogonal properties would be suitable subsequent structural diversification. DFT calculations identified favorable P–F interaction crucial factor from both thermodynamic kinetic viewpoints.

Язык: Английский

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New Opportunities to Access Fluorinated Molecules Using Organophotoredox Catalysis via C(sp³)–F Bond Cleavage

JACS Au, Год журнала: 2025, Номер 5(2), С. 466 - 485

Опубликована: Фев. 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.

Язык: Английский

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E/Z Photoisomerization-Induced Photostability in Benzylcyanocoumarin Dyes and Their Coatings

Опубликована: Янв. 1, 2025

Язык: Английский

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Electrochemical Access to Difluoromethyl Groups: An Overview of Scope, Mechanisms, and Challenges

ACS Catalysis, Год журнала: 2025, Номер unknown, С. 6826 - 6851

Опубликована: Апрель 14, 2025

Язык: Английский

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Visible Light-Promoted Defluorinative Alkylation of Trifluoromethyl Ketones with α-Aminoalkyl Boron Species

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Апрель 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.

Язык: Английский

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Defluorinative Approach for the Synthesis of Chromones via [4 + 2] Annulation of Difluoro Quinone Methide

The Journal of Organic Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Май 1, 2025

We have developed a transition metal-free defluorinative method for 2-(trifluoromethyl)phenol, which facilitates the synthesis of chromones. This reaction features previously unexplored [4 + 2] annulation in situ-generated reactive difluoro quinone methide and 1,3-dicarbonyl compounds. Notably, this distinct mode reactivity applies to diverse array substrates operates under mild conditions, showcasing scalability.

Язык: Английский

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Photocatalytic Dual-Defluorination Thiolation of Trifluoromethyl Hydrazones

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Май 9, 2025

The defluorination of trifluoromethyl groups typically involves breaking one or all three C-F bonds, while selectively cleaving exactly two bonds presents a considerable challenge. In this work, we present method for the sequential hydrazones under photocatalytic conditions, which specific breakage followed by thiolation to yield monofluorinated alkenes containing thiol group. Transforming trifluoromethyl-containing polyfluoroalkyl substances into fluorinated non-PFAS compounds holds potential practical implications.

Язык: Английский

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E/Z photoisomerization-induced photostability in benzylcyanocoumarin dyes and their coatings

Progress in Organic Coatings, Год журнала: 2025, Номер 207, С. 109360 - 109360

Опубликована: Май 31, 2025

Язык: Английский

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Defluorinative Haloalkylation of Unactivated Alkenes Enabled by Dual Photoredox and Copper Catalysis

The Journal of Organic Chemistry, Год журнала: 2024, Номер 89(18), С. 13518 - 13529

Опубликована: Сен. 10, 2024

A three-component defluorinative haloalkylation of alkenes with trifluoromethyl compounds and TBAX (X = Cl, Br) via dual photoredox/copper catalysis is reported. The mild conditions are compatible a wide array activated aromatics bearing diverse substituents, various nonactivated terminal internal alkenes, enabling straightforward access to synthetically valuable γ-gem-difluoroalkyl halides high efficiency. Mechanistic studies indicate that the [Cu] complexes not only serve as XAT catalysts but also facilitate SET reduction groups by photocatalysts. Additionally, resulting alkyl halide products can versatile conversion intermediates for synthesis range compounds.

Язык: Английский

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