Silver-Promoted Three-Component Synthesis of Perfluoroalkenyl Pyrroles through Partial Defluorinative Functionalization of Perfluoroalkyl Halides

Organic Letters, Год журнала: 2024, Номер 26(29), С. 6197 - 6202

Опубликована: Июль 15, 2024

A silver-promoted three-component heterocyclization of alkynes, perfluoroalkyl halides, and 1,3-dinucleophiles was developed for the efficient synthesis privileged (E)-perfluoroalkenyl pyrroles. The reaction proceeded through a rationally designed sequence radical perfluoroalkylation intramolecular defluorinative [3 + 2]-heterocyclization. utility halide as perfluoroalkenyl reagent, by selective controllable functionalization two inert C(sp3)–F bonds at vicinal carbon centers on chain, provides new mode value-added organofluorides starting from easily available low-cost fluorinated feedstock.

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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Three-Component Sulfonylation and Heteroannulation Enabled by 3-Fold Defluorofunctionalization of Trifluoromethyl Enones

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

Опубликована: Фев. 23, 2025

Trifluoromethyl enone emerges as a versatile and multifaceted building block in organic synthesis. A defluorinative heterocyclization reaction of readily available β,β-ditrifluoromethylated enones biocompatible sodium sulfinates has been developed for the modular synthesis densely functionalized furans with regio-defined C2,4-bissulfonyl C3-trifluoromethyl substitutions. This three-component method proceeds through sequential sulfonylation intramolecular O-cyclization, enabling assembly one furan ring, formation C-SO2/C–O bonds, cleavage three C(sp3)-F bonds one-pot manner under transition metal-free conditions. Moreover, obtained product can further react benzyne precursor to generate 1,4-epoxynaphthalene Diels–Alder cycloaddition. The is also distinguished by its broad substrate scope, excellent functional group tolerance, scalability.

Язык: Английский

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Modular Synthesis of Furans with Four Nonidentical Substituents by Aqueous Defluorinative Reaction of Trifluoromethyl Enones with Two Nucleophiles

Organic Letters, Год журнала: 2024, Номер unknown

Опубликована: Дек. 24, 2024

A three-component reaction of trifluoromethyl enones, phosphine oxides, and alcohols in water solution is developed. This defluorinative occurs through a cascade process involving defluorophosphorylation, defluoroalkyloxylation, defluoroheteroannulation, enabling the modular synthesis furans with four distinct substituents: C2-alkyloxy, C3-trifluoromethyl, C4-phosphoryl, C5-(hetero)aryl groups. Moreover, apart from alcohol substrates, scope nucleophiles could be further extended to phenols, azacycles, or sulfonamide.

Язык: Английский

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Selective and Controllable Defluorophosphination and Defluorophosphorylation of Trifluoromethylated Enones: An Auxiliary Function of the Carbonyl Group

Organic Letters, Год журнала: 2023, Номер 25(20), С. 3745 - 3749

Опубликована: Май 11, 2023

The auxiliary function of a carbonyl group in the tunable defluorophosphination and defluorophosphorylation trifluoromethylated enones with P(O)-containing compounds was demonstrated. Controlled replacement one or two fluorine atoms while maintaining high chemo- stereoselectivity achieved under mild conditions, thus enabling diversity-oriented synthesis skeletally diverse organophosphorus libraries─(Z)-difluoro-1,3-dien-1-yl phosphinates, (1Z,3E)-4-phosphoryl-4-fluoro-buta-1,3-dien-1-yl (E)-4-phosphoryl-4-fluoro-1,3-but-3-en-1-ones─in good yields excellent functional tolerance.

Язык: Английский

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“On-water” defluorophosphorylation of trifluoromethylated enones with phosphine oxides

Green Chemistry, Год журнала: 2023, Номер 25(16), С. 6489 - 6497

Опубликована: Янв. 1, 2023

An efficient “on-water” reaction of β-trifluoromethylated enones with phosphine oxides was developed for the preparation phosphorylated gem -difluorodienes excellent Z -selectivity.

Язык: Английский

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Synthesis of Polysubstituted Furans: An Update Since 2019

Asian Journal of Organic Chemistry, Год журнала: 2023, Номер 12(9)

Опубликована: Авг. 7, 2023

Abstract Polysubstituted furans are widespread structural motifs, extensively dispersed in natural products, numerous bioactive compounds, pharmaceuticals, agrochemicals and organic functional materials. Hence, the development of rapid competent methodologies for synthesis multisubstituted has drawn much attention over years. This review summarizes polysubstituted using transition‐metal catalyzed, transition metal‐free, photochemical electrochemical approaches with plausible mechanistic insights. In each reaction, highest yields di‐, tri‐ or tetrasubstituted highlighted some applications methodology towards products biologically active compounds mentioned. The present highlights recent progresses reported from 2019 to 2023.

Язык: Английский

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Na₂S·9H₂O Enabled Defluorodisulfuration and Hydrodefluorination of Perfluorobutyl Tetralones: Synthesis of Trifluoromethyl 1,2-Dithioles

Organic Letters, Год журнала: 2023, Номер 25(23), С. 4388 - 4393

Опубликована: Июнь 2, 2023

An unprecedented defluorocyclization of perfluorobutyl tetralones with Na2S·9H2O was developed for the synthesis trifluoromethyl 1,2-dithioles, which provided chemists novel access to biologically and pharmaceutically relevant organofluorides. Successive C(sp3)–F bond functionalization at perfluoroalkyl chain is vital formation four C–H/C–S/S–S bonds a five-membered S-heterocycle assembly. Cheap, weakly toxic, odorless inorganic sulfide acts as both disulfurating precursor hydrodefluorinating reagent in this tandem multi-bond-interconverting reaction.

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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1,2‐Dichloroethane‐Assisted Defluorinative Ring‐Opening Reaction of DABCO and Polyfluoroalkyl Peroxides: Synthesis of Fluorinated N‐Ethyl Piperazines

Chinese Journal of Chemistry, Год журнала: 2024, Номер unknown

Опубликована: Ноя. 14, 2024

Comprehensive Summary A catalyst‐free and additive‐free ring‐opening reaction of polyfluoroalkyl peroxides, triethylenediamine (DABCO), 1,2‐dichloroethane (DCE) has been developed for the defluorinative synthesis structurally diverse piperazines featuring a fluoroenone framework N ‐chloroethyl‐substituent with high Z ‐stereoselectivity. The success this three‐component is attributed to in situ generation an active 1‐(2‐chloroethyl)‐1,4‐diazabicyclo[2.2.2]octan‐1‐ium (DABCO·DCE) salt, which judiciously acts as formal ‐(2‐chloroethyl)piperazine equivalent coupling less‐studied aliphatic fluorinated substances. Impressively, accomplishes multi‐activation robust C(sp 3 )‐F, )‐Cl, )‐O, )‐N bonds one‐pot process, offering practical platform late‐stage functionalization complex molecules. Furthermore, resulting products can not only serve versatile building blocks heterocycles, but also undergo C—Cl bond displacement transformations ‐, O S ‐nucleophiles.

Язык: Английский

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