Catalysis in the Excited State: Bringing Innate Transition Metal Photochemistry into Play

ACS Catalysis, Год журнала: 2025, Номер unknown, С. 4665 - 4680

Опубликована: Март 5, 2025

Transition metal catalysis is an indispensable tool for organic synthesis that has been harnessed, modulated, and perfected many decades by careful selection of centers ligands, giving rise to synthetic methods with unparalleled efficiency chemoselectivity. Recent developments have demonstrated how light irradiation can also be recruited as a powerful dramatically alter the outcome catalytic reactions, providing access innovative pathways remarkable potential. In this context, adoption photochemical conditions mainstream strategy drive reactions unveiled exciting opportunities exploit rich excited-state framework transition metals applications. This Perspective examines advances in application complexes standalone photocatalysts, exploiting innate reactivity their excited states beyond common use photoredox catalysts. An account relevant examples dissected provide discussion on electronic reorganization, orbitals involved, associated different types states. analysis aims practitioners fundamental principles guiding strategies understand, design, apply light-activation homogeneous synthesis.

Язык: Английский

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Nucleophilic Aromatic Substitution of Halobenzenes and Phenols with Catalysis by Arenophilic π Acids

Accounts of Chemical Research, Год журнала: 2024, Номер 57(15), С. 2194 - 2206

Опубликована: Июль 23, 2024

ConspectusLewis π acids, particularly high-valent transition metals with vacant orbitals, can coordinate unsaturated compounds such as alkynes and alkenes by means of π-bonding. The coordination enhances the electrophilicity bound compounds, thereby facilitating reactions─such nucleophilic addition─that take place at ligated carbon-carbon multiple bonds. This activation phenomenon occurs ligand rather than metal atom, it has been extensively utilized in development catalytic methods. In addition to alkenes, aromatic featuring a phenyl ring be activated an electrophilic transition-metal unit (e.g., Cr(CO)

Язык: Английский

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From aryl chlorides to phenols: Photouranium-catalyzed hydroxylation via water splitting

Chem Catalysis, Год журнала: 2024, Номер 4(7), С. 101027 - 101027

Опубликована: Июнь 12, 2024

Язык: Английский

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Hepatotoxicity of Three Common Liquid Crystal Monomers in Mus musculus: Differentiation of Actions Across Different Receptors and Pathways

Environmental Science & Technology, Год журнала: 2025, Номер unknown

Опубликована: Янв. 13, 2025

Liquid crystal monomers (LCMs) of different chemical structures were widely detected in various environmental matrices. However, their health risk evaluation is lacking. Herein, three representative LCMs selected from 74 LCM candidates upon literature review and acute cytotoxicity evaluation, then Mus musculus exposed to the for 42 days at doses 0.5 50 μg/kg/d investigate hepatotoxicity mechanisms. Phenotypic histopathological results showed that (DTMDPB, MeO3bcH, 5OCB) induced hepatomegaly, only 5OCB fatty liver. DTMDPB MeO3bcH decreased total cholesterol (TCHO) triglyceride (TG) content, whereas increased TCHO, TG, alanine aminotransferase levels. Transcriptome molecular docking analysis revealed by agonizing farnesoid X receptor, resulting disruption unsaturated acid biosynthesis, ascorbic antioxidant pathways, circadian clock homeostasis. promoted inflammation altered acid, primary bile rhythm antagonizing aryl hydrocarbon receptor. antagonized peroxisome proliferator-activated receptors, leading liver caused steroid, cholesterol, terpenoid backbone biosynthesis pathways. This study provides references understanding with selection priority control LCMs.

Язык: Английский

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Photoredox-Catalyzed Nucleophilic Aromatic Substitution of Halophenols with Azoles via Oligomeric Phenylene Oxide Radicals

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Март 6, 2025

Nucleophilic aromatic substitution (SNAr) reactions are widely employed in organic synthesis yet typically require the use of electron-deficient arenes for efficient reactivity. Herein, we report a photocatalytic protocol formal SNAr electron-rich 4-halophenols with azole nucleophiles under mild, redox-neutral conditions. The transformation proceeds via two-stage mechanism consisting initial halophenol oligomerization to produce key oligo(phenylene oxide) intermediate and its subsequent breakdown through enabled by photoredox-catalyzed arene umpolung. Reaction monitoring, stoichiometric control experiments, luminescence quenching data implicate phenoxyl radicals Brønsted acid-activated as reactive species stages, respectively. synthetic utility this method is demonstrated across 17 (pseudo)halophenols bearing variety leaving groups (F, Cl, Br, OMs, OTs) 22 examples.

Язык: Английский

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Visible-Light-Induced Photocatalytic Degradation of Polyvinyl Chloride under Normal Temperature and Pressure via Uranyl Photocatalyst

Industrial & Engineering Chemistry Research, Год журнала: 2025, Номер unknown

Опубликована: Апрель 3, 2025

Язык: Английский

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F- dopants blocking hydroxyl interference: A facile solution for realizing humidity-resistive, selectivity adjustable, highly sensitive In2O3-based gas sensors

Chemical Engineering Journal, Год журнала: 2025, Номер unknown, С. 162338 - 162338

Опубликована: Апрель 1, 2025

Язык: Английский

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Photoredox-Catalyzed Markovnikov Hydroamination of Alkenes with Azoles

Organic Letters, Год журнала: 2024, Номер unknown

Опубликована: Окт. 30, 2024

A visible-light induced intermolecular hydroamination of alkenes with azoles is reported, delivering pharmaceutically valuable N-benzyl in high yields excellent Markovnikov selectivity. Mechanistic studies suggest that the process initiated by energy transfer excited photocatalyst alkenes, followed single electron reduction, protonation, and subsequent oxidation to afford key alkyl carbocation intermediate. This protocol exhibits advantages broad functional group tolerance, atom economy, efficiency, mild reaction conditions.

Язык: Английский

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Photouranium-catalyzed hydroxylation of aryl chlorides via water splitting

Chem Catalysis, Год журнала: 2024, Номер 4(7), С. 101062 - 101062

Опубликована: Июль 1, 2024

Язык: Английский

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Synthesis and Photocatalytic sp3 C-H Bond Functionalization of Salen-Ligand-Supported Uranyl(VI) Complexes

Molecules, Год журнала: 2024, Номер 29(17), С. 4077 - 4077

Опубликована: Авг. 28, 2024

Recent years have seen increasing interest in uranyl(VI) photocatalysis. In this study, uranyl complexes were successfully synthesized from ligands

Язык: Английский

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