Recent advances in the electrochemical generation of 1,3-dicarbonyl radicals from C–H bonds

Organic Chemistry Frontiers, Год журнала: 2023, Номер 10(11), С. 2830 - 2848

Опубликована: Янв. 1, 2023

Recent advances in the electrochemical generation of 1,3-dicarbonyl radicals from C–H bonds and their mechanistic insights synthetic applications have been summarized.

Язык: Английский

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Recent advances in transition metal-mediated trifluoromethylation reactions

Chemical Communications, Год журнала: 2022, Номер 58(75), С. 10442 - 10468

Опубликована: Янв. 1, 2022

Fluorine compounds are known for their abundance in more than 20% of pharmaceutical and agrochemical products mainly due to the enhanced lipophilicity, metabolic stability pharmacokinetic properties organofluorides. Consequently, last decade has seen enormous growth incorporation a trifluoromethyl group into organic motifs. With significance, this review aims provide complete picture transition metal-mediated construction C(sp3, sp2, sp)-CF3 bonds via C-H/X bond functionalization or addition processes both aliphatic aromatic hydrocarbons. Diversified reagents ranging from radical electrophilic nucleophilic trifluoromethylating agents respective mechanisms have been further deliberated comprehensive overview. The coverage on topic is expected make unique beneficial future applications enriching community towards improvements field trifluoromethylation reactions, turn improving propensity development drugs.

Язык: Английский

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Enhanced Three-Component Chloro-/Azido-Fluoroalkylation of Unactivated Alkenes via the Proximity Effect in a Heterogenous Metallaphotocatalyst

ACS Catalysis, Год журнала: 2025, Номер 15(3), С. 2180 - 2191

Опубликована: Янв. 22, 2025

Heterogeneous metallaphotocatalytic chemical transformations employing a recyclable catalyst are highly desirable for organic synthesis. However, the rational design and controlled preparation of well-defined, site-isolated metal/photo bifunctional heterogeneous catalysts to achieve this goal remain significant challenge. In study, we demonstrate covalent attachment homogeneous molecular MnSalen complex (where Salen = N,N′-bis(salicylidene)ethylenediamine) onto surface graphitic carbon nitride (CN) via an amide bond visible-light-driven chloro- azido-fluoroalkylation unactivated alkenes. The linkage between CN not only facilitates electron delocalization enhances light-harvesting capabilities photosensitizer but also exerts proximity effect that markedly ability Mn sites capture alkyl radical intermediates during reaction process. A diverse set alkenes could be efficiently azido-fluoroalkylated their corresponding difunctionalized products in moderate high yields with good functional group compatibility. Furthermore, practicability protocol is illustrated through late-stage diversification various bioactive compounds pharmaceuticals. Notably, integrated photocatalyst demonstrates stability can recycled at least 10 times without loss activity selectivity.

Язык: Английский

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Electrochemically Enabled Carbohydroxylation of Alkenes with H₂O and Organotrifluoroborates

Journal of the American Chemical Society, Год журнала: 2018, Номер 140(48), С. 16387 - 16391

Опубликована: Ноя. 2, 2018

Unprecedented hydroxy-alkynylation and -alkenylation reactions of arylalkenes have been developed through electrochemically enabled addition an organotrifluoroborate reagent H2O across the double bond alkene. The use electrochemistry to promote these oxidative alkene 1,2-difunctionalization not only obviates need for transition-metal catalysts oxidizing reagents but also ensures high regio- chemoselectivity afford homopropargylic or homoallylic alcohols. possibility extending electrochemical difunctionalization strategy other carbo-heterofunctionalization has demonstrated.

Язык: Английский

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Electrochemical Oxidation with Lewis-Acid Catalysis Leads to Trifluoromethylative Difunctionalization of Alkenes Using CF₃SO₂Na

Organic Letters, Год журнала: 2018, Номер 20(23), С. 7396 - 7399

Опубликована: Ноя. 21, 2018

The directly external oxidant-free oxytrifluoromethylation and aminotrifluoromethylation of alkenes have been developed through the constant current electrolysis synergizing with a Lewis-acid catalysis protocol. By using sodium trifluoromethanesulfinate as trifluoromethyl source, method enabled difunctionalization C-C double bonds wide range styrene derivatives.

Язык: Английский

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