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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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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Switchable Multicomponent Cyclization Reactions to Access Fluoroalkylated Dihydropyrimidines and Pyrimidines under Solvent‐Free Conditions

Chinese Journal of Chemistry, Год журнала: 2024, Номер 42(12), С. 1394 - 1398

Опубликована: Фев. 23, 2024

Comprehensive Summary The development of switchable solvent‐free multicomponent reactions to build high‐value‐added products is an important demand for organic synthesis. Herein, we detailed the successful implementation a strategy construction diverse 4‐fluoroalkyl‐1,4‐dihydropyrimidines and 4‐fluoroalkyl‐pyrimidines via solvent/additive‐free [3 + 2 1] annulation, starting from readily available enamines, trifluoroacetaldehyde hydrate or 1‐ethoxy‐2,2‐difluoroethanol amidines hydrochloride. This reaction conforms concept green synthesis, provides new avenue access valuable fluorinated heterocycles.

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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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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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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“On‐Water” Synthesis of Sterically Congested γ‐Ketophosphine Oxides Featuring a CF₃‐ and P(O)‐Tetrasubstituted Carbon Center

Advanced Synthesis & Catalysis, Год журнала: 2023, Номер 365(20), С. 3546 - 3552

Опубликована: Сен. 16, 2023

Abstract The distinctive hydrophobic hydration effect in the aqueous solution contributes to success of phospha‐Michael reaction between β‐CF 3 ‐β,β‐disubstituted enones and diarylphosphine oxides, providing an access biologically relevant γ‐ketophosphine oxides bearing a sterically highly congested CF ‐ P(O)‐tetrasubstituted carbon center. More importantly, resulting products could be further transformed into densely functionalized containing

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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Heteroarylation of Organophosphonium Salts with Indoles in Water: Synthesis of Symmetrical and Unsymmetrical 3,3'‐Bisindolylmethane Derivatives

European Journal of Organic Chemistry, Год журнала: 2024, Номер unknown

Опубликована: Окт. 16, 2024

Abstract A method for the synthesis of symmetrical and unsymmetrical 3,3′‐bis(indolyl)methanes (3,3′‐BIMs) has been developed through direct heteroarylation indolyl‐containing di(hetero)aryl phosphonium salts with indole derivatives in aqueous media. This metal‐free reaction proceeds smoothly under mild conditions, eliminating need hazardous solvents expensive additives/catalysts typically used conventional routes, thereby highlighting synthetic practicality efficiency process. The success this approach is largely attributed to role water as a promoter, facilitating C−P bond functionalization salts. Furthermore, demonstrates broad substrate scope, good functional group tolerance, excellent scalability. Moreover, protocol can also be extended triindolylmethane compound diarylmethylated indole.

Язык: Английский

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