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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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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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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[4+2] Defluorocycloaddition of Perfluoroalkyl Alkynes and Benzylamines: Synthesis of meta-Fluoroalkylated Pyridin-4-amines

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Март 28, 2025

Pyridines represent privileged heterocycles, and the ability to produce fluorinated pyridines from polyfluorinated substances through selective defluorofunctionalization is a new addition their synthesis. Herein, an unprecedented formal [4+2] defluorocycloaddition of perfluoroalkyl alkynes benzylamines under metal-free conditions described. By leveraging functionalization four C(sp3)–F bonds on two vicinal sterically hindered carbons alkynes, diverse array meta-fluoroalkylated pyridin-4-amines were synthesized with good functional group tolerance. The mechanistic studies revealed sequence hydroamination, successive defluorination, 6π-electrocyclization, aromatization, amination.

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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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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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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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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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 defluorinative cyclization of perfluoroalkyl alkenyl iodides with C,N-dinucleophiles: synthesis of (E)-perfluoroalkenyl pyrroles

Green Synthesis and Catalysis, Год журнала: 2024, Номер unknown

Опубликована: Окт. 1, 2024

Язык: Английский

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