Dearomatization of Pyridines: Photochemical Skeletal Enlargement for the Synthesis of 1,2-Diazepines

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(4), С. 2845 - 2854

Опубликована: Янв. 18, 2024

In this report, we developed a unified and standardized one-pot sequence that converts pyridine derivatives into 1,2-diazepines by inserting nitrogen atom. This skeletal transformation capitalizes on the in situ generation of 1-aminopyridinium ylides, which rearrange under UV light irradiation. A thorough evaluation key parameters (wavelength, reaction conditions, activating agent) allowed us to elaborate simple, mild, user-friendly protocol. The model was extrapolated more than 40 examples, including drug derivatives, affording unique 7-membered structures. Mechanistic evidence supports transient presence diazanorcaradiene species. Finally, pertinent transformations products, ring contraction reactions form pyrazoles, were conducted paved way broad application

Язык: Английский

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Recent advances in copper-catalyzed multicomponent reactions with photoinduction

Coordination Chemistry Reviews, Год журнала: 2025, Номер 528, С. 216428 - 216428

Опубликована: Янв. 4, 2025

Язык: Английский

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Divergent Synthesis of F- and CF₃-Containing N-Fused Heterocycles Enabled by Fragmentation Cycloaddition of β-CF₃-1,3-Enynes with N-Aminopyridiniums Ylides

Organic Letters, Год журнала: 2024, Номер 26(6), С. 1255 - 1260

Опубликована: Фев. 7, 2024

The two novel cyclization modes of β-CF

Язык: Английский

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Copper-catalyzed photoredox 1,4-amidocyanation of 1,3-enynes with N-amidopyridin-1-ium salts and TMSCN: Facile access to α-amido allenyl nitriles

Chinese Chemical Letters, Год журнала: 2024, Номер 35(11), С. 109685 - 109685

Опубликована: Март 1, 2024

Язык: Английский

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Cobalt-Promoted Photoredox 1,2-Amidoamination of Alkenes with N-Sulfonamidopyridin-1-ium Salts and Free Amines

Organic Letters, Год журнала: 2024, Номер 26(8), С. 1667 - 1671

Опубликована: Фев. 21, 2024

A cobalt-promoted photoredox 1,2-amidoamination of alkenes with

Язык: Английский

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Photoredox Catalysis for the Synthesis of N‐CF₂H Compounds Using 1‐((N‐(difluoromethyl)‐4‐methylphenyl)‐sulfonamido)pyridin‐1‐ium Trifluoromethanesulfonate

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(30)

Опубликована: Май 26, 2023

Abstract N ‐(difluoromethyl)amino (−NCF 2 H) compounds are of great interest given their unique and underexplored physiochemical properties. The lack structural diversity in NCF H is likely due part to the shortage protocols for efficient installation. Presented herein a new shelf‐stable pyridinium reagent that enables direct installation ‐(difluoromethyl)sulfonamide moiety [N(Ts)CF H)] onto (hetero)arenes alkenes diversification aryl alkyl compounds. described protocol utilizes blue light photoredox catalysis displays broad functional group tolerance with excellent chemoselectivity. Additional transformations applicability towards continuous flow also demonstrated.

Язык: Английский

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Photo-induced cyclization of olefinic amides towards sulfonamidylated iminoisobenzofurans and benzoxazines

Organic Chemistry Frontiers, Год журнала: 2023, Номер 10(14), С. 3479 - 3484

Опубликована: Янв. 1, 2023

A visible-light induced radical cyclization of olefinic amides with easily available N -sulfonylaminopyridinium salts towards iminoisobenzofurans and benzoxazines has been developed.

Язык: Английский

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Photoredox-catalyzed unsymmetrical diamination of alkenes for access to vicinal diamines

Chemical Communications, Год журнала: 2024, Номер 60(25), С. 3413 - 3416

Опубликована: Янв. 1, 2024

Unsymmetrical vicinal diamines have been achieved via the photoredox-catalyzed difunctionalization of alkenes by using N -aminopyridinium salts and nitriles as amination reagents, respectively.

Язык: Английский

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Synthesis of Secondary Amines via Self-Limiting Alkylation

Organic Letters, Год журнала: 2024, Номер 26(23), С. 4926 - 4931

Опубликована: Июнь 4, 2024

N-centered nucleophilicity increases upon alkylation, and thus selective partial alkylation of ammonia primary amines can be challenging: Poor selectivity overalkylation are often observed. Here we introduce N-aminopyridinium salts as surrogates for the synthesis secondary via self-limiting chemistry. Readily available N-aryl-N-aminopyridinium engage in N-alkylation situ depyridylation to afford aryl-alkyl without any products. The method overcomes classical challenges amine by accomplishing transient, highly nucleophilic pyridinium ylide intermediates applied context complex molecular scaffolds. These findings establish synthons synthetic chemistry a strategy control extent alkylation.

Язык: Английский

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The Merger of Halogen Atom Transfer (XAT) and Energy Transfer Catalysis (EnT) for the Modular 1,2-Iminylalkylation of Diazenes

Organic Letters, Год журнала: 2023, Номер 25(38), С. 7009 - 7013

Опубликована: Сен. 14, 2023

The 1,2-iminylalkylation of diazenes using alkyl iodides in combination with an O-benzoyl oxime is reported. In this transformation, acted as a radical precursor and XAT mediator. addition to common iodides, other such iodomethane, iodomethane-d3, trifluoroiodomethane, ethyl difluoroiodoacetate, iodoalkanes containing unprotected hydroxyl amide groups can also serve C-radical precursors the electrophilic acceptors.

Язык: Английский

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