Recent Advances in Visible Light Induced Palladium Catalysis

Angewandte Chemie International Edition, Год журнала: 2023, Номер 63(9)

Опубликована: Ноя. 14, 2023

Visible light-induced Pd catalysis has emerged as a promising subfield of photocatalysis. The hybrid nature radical species enabled wide array radical-based transformations otherwise challenging or unknown via conventional chemistry. In parallel to the ongoing pursuit alternative, readily available precursors, notable discoveries have demonstrated that photoexcitation can alter not only oxidative addition but also other elementary steps. This Minireview highlights recent progress in this area.

Язык: Английский

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Recent advances in three-component radical acylative difunctionalization of unsaturated carbon–carbon bonds

Organic Chemistry Frontiers, Год журнала: 2023, Номер 10(18), С. 4488 - 4515

Опубликована: Янв. 1, 2023

This review highlights the recent advances in radical acylated difunctionalization of unsaturated carbon–carbon bonds and focuses on mechanistic insights these transformations.

Язык: Английский

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Photochemistry in Medicinal Chemistry and Chemical Biology

Journal of Medicinal Chemistry, Год журнала: 2024, Номер 67(6), С. 4322 - 4345

Опубликована: Март 8, 2024

Photochemistry has emerged as a transformative force in organic chemistry, significantly expanding the chemical space accessible for medicinal chemistry. Light-induced reactions enable efficient synthesis of intricate structures and have found applications throughout different stages drug discovery development processes. Moreover, photochemical techniques provide innovative solutions biology, allowing precise spatiotemporal activation targeted delivery. In this Perspective, we highlight already numerous remarkable even more promising future photochemistry chemistry biology.

Язык: Английский

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Catalytic Asymmetric Cascade Dearomatization of Indoles via a Photoinduced Pd‐Catalyzed 1,2‐Bisfunctionalization of Butadienes

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(26)

Опубликована: Апрель 20, 2024

Photoinduced Pd-catalyzed bisfunctionalization of butadienes with a readily available organic halide and nucleophile represents an emerging attractive method to assemble versatile alkenes bearing various functional groups at the allylic position. However, enantiocontrol and/or diastereocontrol in C-C or C-X bond-formation step have not been solved due open-shell process. Herein, we present cascade asymmetric dearomatization reaction indoles via photoexcited 1,2-biscarbonfunctionalization 1,3-butadienes, wherein control on both electrophile part is achieved for first time photoinduced butadienes. This delivers structurally novel chiral spiroindolenines two contiguous stereogenic centers high diastereomeric ratios (up >20 : 1 dr) good excellent enantiomeric 97 3 er). Experimental computational studies mechanism confirmed radical pathway involving excited-state palladium catalysis. The alignment non-covalent interactions between substrate catalyst were found be essential stereocontrol.

Язык: Английский

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Recent advances in C(sp³)–N bond formation via metallaphoto-redox catalysis

Chemical Communications, Год журнала: 2024, Номер 60(50), С. 6340 - 6361

Опубликована: Янв. 1, 2024

In this review, the state-of-the-art advances in radical-involved C(sp 3 )–N bond formation via metallaphotoredox catalysis have been highlighted, which are organized according to different catalytic modes, reaction types, and substrate classes.

Язык: Английский

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Ni-Catalyzed Regioselective Alkylarylation of Unactivated Alkenes in Amines Enabled by Cooperative Ligand Effects of Nitriles and Electron-Deficient Alkenes

Journal of the American Chemical Society, Год журнала: 2025, Номер 147(2), С. 1667 - 1676

Опубликована: Янв. 7, 2025

We report a Ni-catalyzed vicinal alkylarylation of unactivated alkenes in γ,δ- and δ,ε-alkenylamines with aryl halides alkylzinc reagents. The reaction is enabled by amine coordination can use all primary, secondary, tertiary amines. constructs two new C(sp3)-C(sp3) C(sp3)-C(sp2) bonds produces δ- ε-arylamines C(sp3)-branching at the γ- δ-positions. A variety heteroaryl iodides both primary secondary reagents be used as coupling carbon sources. Mechanistic studies suggest that cooperative effect organic nitriles electron-deficient (EDAs) ligands.

Язык: Английский

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Direct Alkylation of Glycine Derivatives via Photoinduced Palladium Catalysis, Utilizing Intermolecular Hydrogen Atom Transfer Mediated by Alkyl Radicals

ACS Catalysis, Год журнала: 2023, Номер 13(24), С. 15652 - 15662

Опубликована: Ноя. 21, 2023

Unveiling the alkyl/Pd hybrid species is a unique sp3-C-centered radical for facilitating intermolecular hydrogen atom transfer (HAT) in development of direct alkylation glycine derivatives. This transformative reaction proceeds smoothly under simple and mild conditions, exhibiting impressive versatility terms substrate scope encompassing both derivatives alkyl bromides while showcasing remarkable tolerance toward diverse functional groups. To shed light on underlying mechanism, extensive investigations involving control experiments, deuterium labeling, clocking, kinetic studies have been conducted. The collected data consistently support pathway formation Pd(I)/alkyl followed by HAT elimination steps that lead to situ imine intermediates, ultimately culminating final stage through addition.

Язык: Английский

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Photoinduced Pd-Catalyzed Formal Asymmetric Allylic Substitution of Piperidine Scaffolds

ACS Catalysis, Год журнала: 2025, Номер unknown, С. 4384 - 4393

Опубликована: Фев. 26, 2025

Язык: Английский

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Mononuclear palladium(I) and palladium(III) coordination compounds

Coordination Chemistry Reviews, Год журнала: 2025, Номер 535, С. 216605 - 216605

Опубликована: Март 17, 2025

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Synergistic Brønsted Base/Photoredox‐Catalyzed Three‐Component Coupling with Malonates to Synthesize δ‐Hydroxy Esters and δ‐Keto Esters

Chinese Journal of Chemistry, Год журнала: 2024, Номер 42(9), С. 957 - 962

Опубликована: Янв. 18, 2024

Comprehensive Summary Multicomponent alkene 1,2‐dicarbofunctionalizations (DCFs) have emerged as a powerful strategy to rapidly incorporate both two carbon subunits across one C—C double bond in step for enhancing molecular complexity and diversity. To the best of our knowledge, there is only report on photoredox‐catalyzed three‐component DCFs with malonates through radical−radical cross‐coupling, while radical‐polar crossover (RPC)‐type were still rare. Herein, we describe redox‐neutral RPC‐type 1,2‐dialkylation styrenes aldehydes synergistic Brønsted base/photoredox catalysis system. This transition‐metal‐free provides an efficient clean approach broad variety δ‐hydroxy esters also features exceptionally mild conditions, wide compatibility substrate scope functional groups, high atomic economy. Moreover, 1,2‐alkylacylation from same starting materials was achieved one‐pot manner such coupling subsequent two‐electron oxidation process, providing set δ‐keto interest pharmaceutical research.

Язык: Английский

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