Organophotoredox-Driven Three-Component Synthesis of β-Trifluoromethyl β-Amino Ketones

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

Опубликована: Янв. 30, 2025

In this work, we present a photoredox three-component reaction that enables the synthesis of medicinally relevant β-trifluoromethyl β-amino ketones from N-trifluoroethylhydroxylamine derivative, styrenes and DMSO. Remarkably, fluoromethyl, difluoromethyl pentafluoroethyl analogues are also accessed using same conditions. The mechanistic investigations, including radical trapping experiments, cyclic voltammetry, Stern-Volmer quenching studies isotope labelling experiments support photoinduced radical/polar crossover Kornblum-type oxidation mechanisms. Finally, applicability organic skeletons is showcased by notable derivatization reactions.

Язык: Английский

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Photocatalytic C(sp³)‐H gem‐Difluoroallylation and Alkylation with Alkenes via a Base‐Assisted Formal 1,2‐Hydrogen Atom Transfer of Amidyl Radicals

Chinese Journal of Chemistry, Год журнала: 2024, Номер 42(18), С. 2203 - 2210

Опубликована: Май 14, 2024

Comprehensive Summary Compared to well‐established 1,5‐HAT of N ‐centered radicals, the synthetic applications 1,2‐HAT process were scarce due high barrier and constrained three‐membered transition state. Here, we have developed a novel C(sp 3 )‐H gem ‐difluoroallylation via base assisted formal amidyl radicals with reductive quenching cycle photocatalyst. This transformation enables efficient formation α‐aminoalkyl showcases good functional group tolerance. Our preliminary mechanistic experiments, along Density Functional Theory (DFT) calculations demonstrate feasibility especially when by base. Furthermore, our method also succeeds in Giese addition electron‐deficient alkenes as well styrene.

Язык: Английский

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Recent advancements in visible-light-induced direct C(3)–H functionalization of quinoxalin-2(1H)-ones

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

Опубликована: Дек. 1, 2024

Язык: Английский

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Nucleophilic addition of bulk chemicals with imines using N-functionalized hydroxylamine reagents as precursors

Nature Communications, Год журнала: 2025, Номер 16(1)

Опубликована: Янв. 2, 2025

C–C and C–X bond forming reactions are essential tools in organic synthesis, constantly revolutionizing human life. Among the key methods for constructing new chemical bonds nucleophilic addition involving imines. However, inherent challenges synthesizing storing imines have stimulated interest designing stable precursors, which generates situ during reaction. This approach offers a promising alternative to traditional strategies holds significant potential future applications. Here we report direct general of with cost-effective feedstocks easily accessible nucleophiles, specifically utilizing N‑functionalized hydroxylamine reagents as bench-stable precursors. methodology streamlines synthesis various products, such amino acid derivatives, through wide range reaction types, including C–C, C–N, C–O, C–S constructions. Mechanistic studies DFT calculations provide insights into plausible mechanism that supports in-situ imine formation. The stimulate precursors can generate Here, authors N functionalized

Язык: Английский

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Visible Light-Induced Sequential Nitrogen Insertion and Benzotriazolation of Quinoxaline-2(1H)-ones

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Фев. 3, 2025

Herein, we report a visible light-mediated sequential reaction involving in situ generation of benzotriazole from benzene-1,2-diamine and tert-butyl nitrite via nitrogen insertion concomitant cross-coupling with quinoxaline-2(1H)-ones C-N bond formation one pot. This protocol uses metal-free mild conditions demonstrated 36 examples ≤80% yield wide functional group tolerance.

Язык: Английский

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Nitrogen-Based Organofluorine Functional Molecules: Synthesis and Applications

Chemical Reviews, Год журнала: 2025, Номер unknown

Опубликована: Апрель 22, 2025

Fluorine and nitrogen form a successful partnership in organic synthesis, medicinal chemistry, material sciences. Although fluorine-nitrogen chemistry has long rich history, this field received increasing interest made remarkable progress over the past two decades, driven by recent advancements transition metal organocatalysis photochemistry. This review, emphasizing contributions from 2015 to 2023, aims update state of art synthesis applications nitrogen-based organofluorine functional molecules chemistry. In dedicated sections, we first focus on fluorine-containing reagents organized according type groups attached nitrogen, including N-F, N-RF, N-SRF, N-ORF. review also covers nitrogen-linked building blocks, catalysts, pharmaceuticals, agrochemicals, underlining these components' broad applicability growing importance modern

Язык: Английский

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Visible-Light-Driven Tandem Cyclization of o-Hydroxyaryl Enaminones: Access to 3-(α-Arylsulfonamido)trifluoroethyl Chromones

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

Опубликована: Апрель 22, 2025

A visible-light-driven intermolecular tandem α-amidotrifluoroethylation/cyclization of enaminones using a previously unreported N-trifluoroethylaminopyridinium salt was achieved in the absence transition metal catalysts or bases. Notable features this synthetic method include mild conditions, high selectivity, excellent functional group compatibility, and satisfactory yields. Preliminary mechanistic studies indicate that reaction proceeds via radical pathway, involving an situ generated N-trifluoroethyl radical, followed by 1,2-H shift.

Язык: Английский

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Visible-Light-Induced C–H Alkylation of 1,2,4-Triazine-3,5(2H,4H)-diones via Infrequent 1,2-Hydrogen-Atom Transfer

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

Опубликована: Май 19, 2025

1,2,4-Triazine-3,5(2H,4H)-diones are widely present in various drug molecules and bioactive molecules. A visible-light-driven C-H alkylation of 1,2,4-triazine-3,5(2H,4H)-diones via 1,2-hydrogen-atom transfer (1,2-HAT) amide radicals is first reported, providing an environmentally friendly sustainable pathway to enrich the structural functional diversity 1,2,4-triazine-3,5(2H,4H)-diones. This novel protocol characterized by mild metal-free reaction conditions, operationally simple method, good group tolerance. To our delight, other heterocycles, such as isoquinoline coumarin, also undergo reactions construct C(sp2)-C(sp3) bonds infrequent 1,2-HAT under current conditions.

Язык: Английский

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Recent Advances in Photo-promoted Generalized C3-H Alkylation of Quinoxalin-2(1H)-ones

Organic & Biomolecular Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

Recent advances in the photo-promoted C3–H alkylation reaction of quinoxalin-2(1 H )-ones with different agents.

Язык: Английский

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Photoexcited Copper-Catalyzed Difunctionalization of Alkenes for the Synthesis of 2,5-Diamino Acid Derivatives via Uncommon 1,2-Hydrogen Atom Transfer of Amidyl Radicals

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Май 25, 2025

Compared with 1,5-hydrogen atom transfer (1,5-HAT) processes, 1,2-HAT processes have been reported less frequently. And, the synthesis of 2,5-diamino acid derivatives via a mild photocatalytic approach has not yet. Herein, we report photoexcited copper-catalyzed difunctionalization alkenes for uncommon 1,2-HAT. The potential synthetic merit this reaction is proven through scale-up reaction. Notably, new protocol successfully applied to obtain series derivatives.

Язык: Английский

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