Sulfinate-Promoted Defluorinative Cyclization of Polyfluoroalkyl Tetralones Enabled by Photocatalysis

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Фев. 3, 2025

A Ru-catalyzed defluorinative cyclization of polyfluoroalkyl tetralones has been developed under visible-light irradiation for the precise assembly γ-pyrones featuring α-perfluoroalkyl and β-fluorine substituents. Selective functionalization five C(sp3)–F bonds at three carbon sites on perfluoroalkyl chain provides a new mode utilizing polyfluorides as versatile synthons to access difficult-to-obtain heterocyclic scaffolds. Moreover, sulfinate salt serves dual roles an oxygen source creating carbonyl group defluorinating promoter.

Язык: Английский

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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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Defluorinative Cyclization of Enamides with Fluoroalkyl Halides Through Two Vicinal C(sp³)─F Bonds Functionalization

Advanced Science, Год журнала: 2024, Номер unknown

Опубликована: Дек. 31, 2024

Abstract Introducing distinctive functional groups to expand the structural diversity and improve intrinsic properties of parent molecules has been an essential pursuit in organic chemistry. By using perfluoroalkyl halide (PFAH) as a nontraditional, readily available, ideal 1,2‐difluoroalkenyl coupling partner, defluorinative cyclization reaction enamides for construction fluoroalkenyl oxazoles is first developed. The selective controllable two‐fold cleavage vicinal C(sp 3 )─F bonds PFAH not only enables introduction specific moiety with ease but also results functionalization two 2 )─H without need metal catalyst, photocatalyst, oxidant, or light. method can be applied late‐stage modification complex molecules, synthesis biological‐relevant oxazole analoges, scale‐up synthesis, which all further highlight real‐world utility this protocol. Mechanistic studies reveal that possibly proceeds through radical perfluoroalkylation, consecutive C─F bond heterolytic cleavage, process. In addition, situ formed may serve hydrogen abstractor.

Язык: Английский

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Perfluoroalkyl Editing of Fluoroalkynes: Chemo-, Regio-, and Stereoselective Synthesis of (E)-(2-Amino-fluoroalkenyl)pyrimidines

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Фев. 26, 2025

A chemo-, regio-, and stereoselective condensation reaction of perfluoroalkyl alkynes (PFAAs), (CH2O)n, (NH4)2CO3 through the cleavage five inert C(sp3)-F bonds at three distinct carbon sites, thereby establishing an unprecedented platform for synthesizing structurally unique (E)-(2-amino-fluoroalkenyl)pyrimidines, is first developed. Remarkably, this features mild conditions, good compatibility with various functional groups, excellent E-stereoselectivity, late-stage modification complex molecules, scalability, versatile synthetic transformations resulting heterocyclic compounds.

Язык: Английский

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Intermolecular Defluorinative 1,2-Diamination of Fluoroalkenyl Iodides with Sulfonamides: Synthesis of Acyclic and Cyclic Fluorinated 1,2-Enediamines

Organic Chemistry Frontiers, Год журнала: 2024, Номер unknown

Опубликована: Ноя. 13, 2024

An intermolecular defluorinative vicinal diamination protocol employing fluoroalkenyl iodides and sulfonamides for the efficient synthesis of a series acyclic cyclic fluorinated 1,2-enediamines has been developed.

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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Palladium-Catalyzed Regioselective Monofluoroallylation of Indoles with gem-Difluorocyclopropanes

Organic Letters, Год журнала: 2024, Номер 26(32), С. 6905 - 6909

Опубликована: Авг. 1, 2024

We present a palladium-catalyzed ring-opening reaction that induces indoles to cross-couple with gem-difluorocyclopropanes. The proceeds through domino process of C–C bond activation and C–F elimination, followed by C–C(sp2) coupling produce various 2-fluoroallylindoles. This method is characterized its high functional group tolerance, good yields regioselectivity, under base-free conditions. synthetic utility the products illustrated functionalization NH C2 positions indole scaffold.

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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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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Synthesis of Tetrasubstituted Pyrroles via DBU-Mediated Cyclization of Unactivated Propargyl Tertiary Amines

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

Опубликована: Март 10, 2025

Compared with the well-developed cyclization of functionalized propargylamines, use unactivated tertiary propargylamines to access pyrroles remains challenging. Herein, we report an efficient method for constructing tetrasubstituted via a DBU-mediated intramolecular cycloaddition N-alkyl propargylamines. This reaction employs dihydropyrrole intermediates, followed by oxidation produce in presence 2,3-dichloro-5,6-dicyano-p-benzoquinone. In addition, broad substrate scope, high atom economy, selectivity, and simple operation are also advantages this protocol.

Язык: Английский

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