Photoinduced copper-catalyzed C–N coupling with trifluoromethylated arenes

Nature Communications, Год журнала: 2023, Номер 14(1)

Опубликована: Дек. 14, 2023

Selective defluorinative functionalization of trifluoromethyl group (-CF3) is an attractive synthetic route to the pharmaceutically privileged fluorine-containing moiety. Herein, we report a strategy based on photoexcited copper catalysis activate C-F bond di- or trifluoromethylated arenes for divergent radical C-N coupling with carbazoles and aromatic amines. The use different ligands can tune reaction products diversity. A range substituted, structurally diverse α,α-difluoromethylamines be obtained from via carbazoles, while interesting double ready difluoromethylated arenes. Based this success, carbazole-centered PNP ligand designed optimal ligand, enabling copper-catalyzed construction imidoyl fluorides amines through functionalization. Interestingly, 1,2-difluoroalkylamination styrenes also developed, delivering γ,γ-difluoroalkylamines, bioisostere β-aminoketones, in synthetically useful yields. DFT studies reveal inner-sphere electron transfer mechanism Cu-catalyzed selective activation C(sp3)-F bonds.

Язык: Английский

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Nickel-Catalyzed Direct Cross-Coupling of Unactivated Aryl Fluorides with Aryl Bromides

Organic Letters, Год журнала: 2023, Номер 25(29), С. 5525 - 5529

Опубликована: Июль 17, 2023

A nickel-catalyzed direct cross-coupling of unactivated aryl fluorides with bromides is realized. The one-pot reaction, which avoids the use preformed and sensitive organometallic reagents, proceeds effectively via C-F bond cleavage at room temperature in THF presence phosphine ligand magnesium powder (with or without TMSCl) to produce desired biaryls modest good yields.

Язык: Английский

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Water-promoted defluorinative synthesis of fluoroalkylated 1,5-diazapentadienes by using (NH₄)₂CO₃ as an NH₂ and NH source

Green Chemistry, Год журнала: 2023, Номер 25(23), С. 9672 - 9679

Опубликована: Янв. 1, 2023

A H 2 O-promoted and (NH 4 ) CO 3 -enabled defluoroiminization reaction of fluoroalkyl alkenes for the synthesis fluoroalkylated 1,5-diazapentadienes has been developed.

Язык: Английский

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Combining (CH₂O)_n and (NH₄)₂CO₃ as a Formamidine Equivalent for “Four-in-One” Synthesis of Fluoroalkylated 2-H-Pyrimidines

Organic Letters, Год журнала: 2024, Номер 26(33), С. 7078 - 7082

Опубликована: Авг. 9, 2024

Multicomponent reactions hold the potential to maximize synthetic efficiency in preparation of diverse and complex molecular scaffolds. An unprecedented formal [3+1+1+1] annulation approach for one-step synthesis fluoroalkylated 2-H-pyrimidines commencing from perfluoroalkyl alkenes, paraformaldehyde, ammonium carbonate is described. By harnessing readily accessible (CH2O)n cheap (NH4)2CO3 as a formamidine surrogate, this method effectively replaces traditionally preformed amidines with pyrimidine assembly. The multicomponent reaction proceeds step-economical, operationally simple, metal-free, additive-free manner, featuring broad substrate scope, excellent functional group compatibility, scalability. elaboration obtained 2-H-pyrimidine further demonstrated alkylation vinylation its C2 position.

Язык: Английский

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Direct Fluoroacylation of Indole with Perfluoroalkyl Iodides

Organic Letters, Год журнала: 2023, Номер 25(29), С. 5548 - 5551

Опубликована: Июль 18, 2023

Functionalization of perfluoroalkyl compounds has shown huge potential in synthetic chemistry and drug development. Herein, we report a one-pot tandem perfluoroalkylation-defluorination reaction indole, iodide, water the presence Na2S2O4. A wide array indole derivatives were efficiently accessed with good yields under mild conditions. The is believed to undergo perfluoroalkylation follow defluorination hydrolysis pathway. This study represents an alternative approach for functionalization.

Язык: Английский

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Organic Base-Catalyzed Cascade Reaction of CF₃–Iminopropargylic Alcohols with Carboxylic Acids: an Approach to β-CF₃ β-Aminoenones

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

Опубликована: Фев. 6, 2025

A novel approach to the synthesis of β-CF3 β-aminoenones by organic amine base-catalyzed reaction CF3-iminopropargylic alcohols with carboxylic acids is reported. The advantages protocol are ease operation, available starting materials, and simple tertiary catalysts.

Язык: Английский

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Water-Involved 1,3-Aminoxylation of Fluoroalkenes: Chemo-, Regio-, and Stereoselective Synthesis of β-Fluoroacyl Vinylamines

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

Опубликована: Апрель 9, 2025

Perfluoroalkyl alkenyl iodides (PFAIs) are emerging as highly reactive, storage-stable, and multifunctional fluoroalkyl-bearing reagents, facilitating the manufacture of value-added organofluorides through multi-halo-functionalization. Herein, we developed a water-involved 1,3-aminoxylation PFAIs with sulfonamides for chemo-, regio-, Z-stereoselective synthesis valuable β-fluoroacyl vinylamines. This reaction proceeded via sequential deiodoamination defluoroxylation process under transition-metal-free conditions, featuring broad substrate scope good functional group tolerance. Compared to reported methods, some drawbacks, such multistep manipulation, harsh need expensive catalysts, use toxic/sensitive could be eliminated. Furthermore, synthetic potential this method was demonstrated scale-up synthesis, postfunctionalization complex molecules, ready transformation products.

Язык: Английский

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Synthesis of trans‐2‐(Disubstituted‐amino)alkenyl Polyoxyperfluoroalkyl Ketones from Tertiary Amines and Perfluoroalkyl Ether Carboxylates Featuring “–CF₂O–” Units^†

Chinese Journal of Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Апрель 25, 2025

Comprehensive Summary A one‐pot transformation of aliphatic and aromatic tertiary amines to novel fluorinated enaminones has been developed, utilizing perfluoroalkyl ether carboxylates (PFECA salts) featuring “–CF 2 O–” units as the fluorine‐containing reagents. Carbonyl fluoride, acyl fluorides anhydrides by thermal decomposition these PFECA salts were proposed act key active species that trigger tandem oxidation–acylation process amines, through enamine intermediates.

Язык: Английский

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Defluorinative functionalization of perfluoroalkyl alkenes with ureas: synthesis of C4-perfluoroalkenyl 2-imidazolones

Organic Chemistry Frontiers, Год журнала: 2024, Номер 11(19), С. 5538 - 5544

Опубликована: Янв. 1, 2024

A defluorinative 1,2,3,4-tetrafunctionalization of perfluoroalkyl alkenes with readily available ureas via multi-bond interconversion at four carbon sites has been developed for the synthesis perfluoroalkenyl 2-imidazolones.

Язык: Английский

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Transition‐Metal‐Free Carbonyl Reduction and Hydrodefluorination of β‐Trifluoromethyl Enones with Hydrosilanes: Synthesis of gem‐Difluorovinyl Alcohols

European Journal of Organic Chemistry, Год журнала: 2024, Номер 27(23)

Опубликована: Апрель 20, 2024

Abstract A tandem carbonyl reduction and hydrodefluorination of β‐trifluoromethyl enones with hydrosilanes under transition‐metal‐free conditions was developed for the synthesis a variety valuable gem ‐difluorovinyl alcohols. The hydrosilane could act as both reductive agent C(sp 3 )‐F bond‐breaking promoter mild reaction conditions. Synthetically useful organofluorides, such ‐fluorophosphine alkene, ketone, fluorinated dihydrofuran derivatives be readily constructed by further transformations obtained Moreover, method features conditions, operational simplicity, excellent functional group tolerance, scalability.

Язык: Английский

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