Synthesis, Characterization, and Catalytic Activity of Ni(0) (DQ)dtbbpy, an Air-Stable, Bifunctional Red-Light-Sensitive Precatalyst

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 5, 2025

Despite a well-established and growing body of work on nickel(0) precatalysts, the potential complexes as bifunctional precatalysts remains underexplored. In this study, we synthesized, characterized, evaluated catalytic activity (Ni(0)(DQ)dtbbpy), bifunctional, red-light-sensitive, air-stable complex. Owing to its unique photophysical properties, it effectively catalyzed etherification amination aryl bromides under 620–630 nm light irradiation, functioning both photocatalyst an active metal catalyst. Mechanistic studies density functional theory (DFT) calculations further confirmed exceptional absorption properties Ni(0)(DQ)dtbbpy in red-light region, well electron transfer process triggered by irradiation.

Language: Английский

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Precise synthesis of advanced polyarylamines for efficient perovskite solar cells

Nature Materials, Journal Year: 2025, Volume and Issue: unknown

Published: April 3, 2025

Language: Английский

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Chemoselective Synthesis of 3-Bromomethyloxindoles via Visible-Light-Induced Radical Cascade Bromocyclization of Alkenes

Organic Letters, Journal Year: 2024, Volume and Issue: 26(18), P. 3923 - 3928

Published: April 25, 2024

A novel visible-light-induced radical cascade bromocyclization of N-arylacrylamides has been accomplished. This reaction overcomes the overbromination at benzene rings suffered in traditional electrophilic reactions, thus enabling first highly chemoselective synthesis valuable 3-bromomethyloxindoles. The combination pyridine and anhydrous medium is identified as key factor for high chemoselectivity current photoreaction system, which might work by suppressing situ generation low-concentration Br2 from N-bromosuccinimide. Moreover, mild conditions ensure a wide range new desired products with excellent functional group tolerance.

Language: Английский

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1,2-Acylcyanation of Styrenes by Photoinduced Nickel Catalysis to Generate Acyl Radicals from Acyl Fluorides

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: March 25, 2025

We report herein a photoinduced nickel-catalyzed 1,2-acylcyanation of styrenes with acyl fluorides and trimethylsilyl cyanide (TMSCN). Nickel(II) complexes, formed from nickel(0) complexes fluorides, are photoexcited to generate radicals via ligand-to-metal charge transfer (LMCT) process. This transformation proceeds under mild conditions thus can be applied the late-stage functionalization (LSF) natural product derivatives. Synthetic derivatizations show utility products. The preparation aza-DIPYs is also demonstrated.

Language: Английский

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Defluorinative Haloalkylation of Unactivated Alkenes Enabled by Dual Photoredox and Copper Catalysis

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(18), P. 13518 - 13529

Published: Sept. 10, 2024

A three-component defluorinative haloalkylation of alkenes with trifluoromethyl compounds and TBAX (X = Cl, Br) via dual photoredox/copper catalysis is reported. The mild conditions are compatible a wide array activated aromatics bearing diverse substituents, various nonactivated terminal internal alkenes, enabling straightforward access to synthetically valuable γ-gem-difluoroalkyl halides high efficiency. Mechanistic studies indicate that the [Cu] complexes not only serve as XAT catalysts but also facilitate SET reduction groups by photocatalysts. Additionally, resulting alkyl halide products can versatile conversion intermediates for synthesis range compounds.

Language: Английский

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Modular synthesis of 3,3-disubstituted oxindoles from nitrones and acrylic acids

Organic & Biomolecular Chemistry, Journal Year: 2024, Volume and Issue: 22(31), P. 6282 - 6287

Published: Jan. 1, 2024

We developed a modular synthesis for 3,3-disubstituted oxindoles, utilising readily accessible nitrones and acrylic acids. This approach facilitates the preparation of diverse array oxindoles through variation starting materials. demonstrated applicability this method gram-scale reaction esermethole.

Language: Английский

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Palladium-Catalyzed Decarbonylative Nucleophilic Halogenation of Acyl Fluorides and Chlorides: Synthesis of Aryl Halides via Reductive Elimination of the C–X (X = I, Br, and Cl) Bond and Mechanistic Implications

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(16), P. 11905 - 11917

Published: July 25, 2024

Aryl halides are widely recognized as crucial and versatile feedstocks for organic synthesis. However, in palladium-catalyzed reactions, while oxidative addition of carbon–halogen bonds is thermodynamically favorable, the reverse reaction─reductive elimination with formation bonds─poses a significant challenge. As part conducting series decarbonylative transformations acyl halides, we developed nucleophilic halogenation fluorides chlorides through Pd-mediated reductive C–X bond. These reactions enable synthesis aryl iodides, bromides, using alkali metal halides. Regarding reaction mechanism, Xantphos ligand emerges factor promoting elimination, leading to stable Pd(0) intermediate an adduct trans-(Xantphos)Pd(ArCO)X. Two proposed mechanisms involve Xantphos-promoted outer-sphere substitution direct transhalogenation between In latter or react form corresponding iodides bromides situ under mild conditions decarbonylation, yielding desired via unimolecular fragment coupling. Importantly, it evident that controlling rate halide appropriate combination substrates success this reaction. Indeed, found gradual iodide pivotal managing undesired generation I2, known catalyst poison. This observation enables us fine-tune conditions, thereby improving selectivity transformation. result, achieve enhanced yields final products establish more sustainable robust catalytic processes. advancement not only boosts applicability reliability our synthetic methodology but also underscores potential broader adoption

Language: Английский

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Visible‐Light‐Mediated Activation of Remote C(sp³)−H Bonds by Carbon‐Centered Biradical via Intramolecular 1,5‐ or 1,6‐Hydrogen Atom Transfer

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(38)

Published: June 21, 2024

Abstract In this study, we introduce a novel intramolecular hydrogen atom transfer (HAT) reaction that efficiently yields azetidine, oxetane, and indoline derivatives through mechanism resembling the carbon analogue of Norrish‐Yang reaction. This process is facilitated by excited triplet‐state carbon‐centered biradicals, enabling 1,5‐HAT suppressing critical 1,4‐biradical intermediates from undergoing Norrish Type II cleavage reaction, pioneering unprecedented 1,6‐HAT reactions initiated alkenes. We demonstrate synthetic utility compatibility method across various functional groups, validated scope evaluation, large‐scale synthesis, derivatization. Our findings are supported control experiments, deuterium labeling, kinetic studies, cyclic voltammetry, Stern–Volmer density theory (DFT) calculations.

Language: Английский

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Visible‐Light‐Mediated Activation of Remote C(sp3)‐H Bonds by Carbon‐Centered Biradical via Intramolecular 1,5‐ or 1,6‐Hydrogen Atom Transfer

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(38)

Published: June 21, 2024

In this study, we introduce a novel intramolecular hydrogen atom transfer (HAT) reaction that efficiently yields azetidine, oxetane, and indoline derivatives through mechanism resembling the carbon analogue of Norrish-Yang reaction. This process is facilitated by excited triplet-state carbon-centered biradicals, enabling 1,5-HAT suppressing critical 1,4-biradical intermediates from undergoing Norrish Type II cleavage reaction, pioneering unprecedented 1,6-HAT reactions initiated alkenes. We demonstrate synthetic utility compatibility method across various functional groups, validated scope evaluation, large-scale synthesis, derivatization. Our findings are supported control experiments, deuterium labeling, kinetic studies, cyclic voltammetry, Stern-Volmer density theory (DFT) calculations.

Language: Английский

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Homoleptic Organolanthanum-Catalyzed Carbohalogenation

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(36), P. 25361 - 25370

Published: Aug. 27, 2024

Metal-halogen exchange reactions are fundamental processes in chemistry that transform organic halides into organometallic reagents. However, using these to build intricate structures a cascade manner, especially catalytic mode, has been challenge. In this study, we introduce homoleptic organolanthanum catalyst initiate lanthanum-halogen and intramolecular carbohalogenation. The pathway can be achieved through metal-halogen carbometalation, followed by the extraction of halogen atoms from starting materials. Our approach offers flexible sustainable way create variety useful compounds, showcasing its potential chemical synthesis.

Language: Английский

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