Picking Two out of Three: Defluorinative Annulation of Trifluoromethyl Alkenes for the Synthesis of Monofluorinated Carbo‐ and Heterocycles

The Chemical Record, Год журнала: 2024, Номер 24(3)

Опубликована: Янв. 22, 2024

Abstract The increasing demand of organofluorine compounds in medicine, agriculture, and materials sciences makes sophisticated methods for their synthesis ever more necessary. Nowadays, not only the C−F bond formation but also selective cleavage readily available poly‐ or perfluorine‐containing have become powerful tools effective compounds. defluorinative cross‐coupling trifluoromethyl alkenes with various nucleophiles radical precursors an S N 2’ manner is a convergent route to access gem ‐difluoroalkenes, which turn react via V‐type reaction. If V reactions occur intramolecularly, dual allows facile assembly monofluorinated cyclic skeletons structural complexity diversity. In this personal account, we summarized advances field on basis coupling cyclization partners, including binucleophiles, alkynes, diradical bearing nucleophilic site. Accordingly, annulation can be achieved by base‐mediated sequential 2′/S reactions, transition metal catalyzed mediated photoredox catalysis, combination photocatalytic context seminal works others field, concise summary contributions authors offered.

Язык: Английский

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“On-water” defluorinative cyclization of trifluoromethyl enones with phosphine oxides: synthesis of polysubstituted furans

Organic Chemistry Frontiers, Год журнала: 2024, Номер 11(14), С. 3974 - 3981

Опубликована: Янв. 1, 2024

A defluorinative cyclization of readily available trifluoromethyl enones with phosphine oxides for the synthesis polysubstituted furans is developed in a pure water solution.

Язык: Английский

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Electrochemical N-acylation and N-α-ketoacylation of sulfoximines via the selective decarboxylation and dehydration of α-ketoacids

Green Chemistry, Год журнала: 2023, Номер 25(21), С. 8838 - 8844

Опубликована: Янв. 1, 2023

We describe an electrochemical N -acylation and -α-ketoacylation of sulfoximines via the selective decarboxylation dehydration α-ketoacids using electricity as a “traceless” oxidant α-ketoacid “acyl” or “α-ketoacyl” source.

Язык: Английский

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Multi-functionalization of β-trifluoromethyl enones enabled 2,3-dihydrofuran synthesis

Organic Chemistry Frontiers, Год журнала: 2024, Номер 11(18), С. 5144 - 5150

Опубликована: Янв. 1, 2024

A transition-metal-free multi-functionalization reaction of β-trifluoromethyl enones and azacycles is first developed for the synthesis valuable amino-2,3-dihydrofuran derivatives.

Язык: Английский

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Construction of 3,6-Difluoropyridones via a Double Defluorinative [3 + 3] Annulation of α-Fluoro-α-sulfonylacetamides with 2-CF₃-Alkenes

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Янв. 8, 2025

A remarkably simple and efficient double defluorinative [3 + 3] annulation approach involving N-phenyl-α-fluoro-α-phenylsulfonylacetamide 2-CF3-alkenes to access N-phenyl-3,6-difluoropyridone derivatives has been achieved. The key the success of this single-step synthesis difluoropyridones is strategic utilization for consecutive allylic vinylic substitution reactions a desulfonylation cascade. We could also show that these serve as versatile platform C-6-selective functionalizations.

Язык: Английский

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Photoredox Catalyzed Synthesis of gem-Difluoroalkenes and Monofluorinated Cyclooctenes via 1,5-HAT Process

Organic Letters, Год журнала: 2024, Номер 26(21), С. 4548 - 4553

Опубликована: Май 17, 2024

gem-Difluoroalkenes and monofluorinated cycloalkenes have emerged as basic structural units in a variety of bioactive molecules natural products. Thus, developing straightforward efficient methods for synthesizing fluorinated alkene compounds is considerable significance. Herein, we disclose visible-light-induced defluorination 2-trifluoromethyl-1-alkene via 1,5-HAT process using N-alkoxyphtalimides both radical precursor potential nucleophile. The mild stepwise reaction leads to structurally diverse gem-difluoroalkenes cyclooctenes with high efficiency, respectively.

Язык: Английский

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Base-Mediated Regioselective [3 + 3] Annulation of Alkylidene Malononitriles with Trifluoromethyl Alkenes via Dual C–F Bond Cleavage

Organic Letters, Год журнала: 2024, Номер 26(35), С. 7452 - 7456

Опубликована: Авг. 26, 2024

A base-mediated regioselective [3 + 3] annulation of alkylidene malononitriles with trifluoromethyl alkenes was described. The reaction proceeds through sequential intermolecular SN2′ and intramolecular SNV-type cyclization by cleaving dual C–F bonds in a group, which discriminate multiple carbon-nucleophilic sites using single base. Various bicycles bearing monofluorocyclohexene motif were assembled from readily available starting materials under mild conditions via one-pot cascade approach.

Язык: Английский

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Divergent Synthesis of Benzo[4,5]imidazo[2,1-b][1,3]thiazines and α-Trifluoromethyl-β-arylthio Tertiary Alcohols from 2-Mercaptobenzimidazoles and α-CF₃ Alkenes

Organic Letters, Год журнала: 2024, Номер 26(44), С. 9610 - 9616

Опубликована: Окт. 25, 2024

An efficient and metal-free approach for the divergent synthesis of 2-fluoro-3-aryl-4H-benzo[4,5]imidazo[2,1-b][1,3]thiazines α-trifluoromethyl-β-arylthio tertiary alcohols from 2-mercaptoimidazoles α-CF3 alkenes has been developed. The chemoselectivity was well controlled by base or light; a series were afforded via base-mediated sequential SN2′- SNV-type reactions. Meanwhile, could be selectively achieved through visible-light-driven electron donor–acceptor (EDA) complex-initiated radical cascade thiolation/hydroxylation in absence base, transition metal, external photocatalyst.

Язык: Английский

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Palladium‐Catalyzed Domino Reaction for the Synthesis of 3‐Amino 1,2,4‐Benzothiadiazine 1,1‐Dioxides

Advanced Synthesis & Catalysis, Год журнала: 2023, Номер 366(4), С. 717 - 724

Опубликована: Окт. 18, 2023

Abstract A palladium‐catalyzed domino reaction of 2‐azidosulfonamides and isocyanides enables the synthesis 3‐amino‐substituted 1,2,4‐benzothiadiazine 1,1‐dioxides at room temperature. By applying commercially available Pd(dba) 2 in catalyst loadings as low 1.0 mol%, a variety 21 differently substituted H ‐1,2,4‐benzothiadiazine can be prepared within h. Moreover, developed protocol gives access to related 4 heterocycles.

Язык: Английский

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Transition-Metal-Free Hydrodefluoroamination of Trifluoromethyl Enones for the Synthesis of α-Fluoroenamides

The Journal of Organic Chemistry, Год журнала: 2024, Номер 89(14), С. 10299 - 10310

Опубликована: Июль 2, 2024

A three-component strategy was developed to enable hydrodefluoroamination of β-trifluoromethyl enones by selectively activating two C(sp3)-F bonds in the trifluoromethyl group. The method involved a sequence carbonyl reduction, hydrodefluorination, and defluoroamination under transition-metal-free conditions. Synthetically useful (E)-stereospecific α-fluoroenamides were obtained good yields with diverse functional group tolerance, which could be easily transformed into valuable organofluorides heterocycles. auxiliary exerts both electronic steric impacts on CF3-alkenes, allowing for controllable selective defluorination.

Язык: Английский

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