5,12-Dihydroquinoxalino[2,3-b] quinoxaline-based porous organic polymer as photocatalyst for visible-light-driven cross-coupling reactions

Journal of Catalysis, Год журнала: 2025, Номер unknown, С. 115972 - 115972

Опубликована: Янв. 1, 2025

Язык: Английский

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Excited-State Nickel-Catalyzed Amination of Aryl Bromides: Synthesis of Diphenylamines and Primary Anilines

Organic Letters, Год журнала: 2024, Номер 26(8), С. 1657 - 1661

Опубликована: Фев. 21, 2024

Excited-state nickel-catalyzed C–N cross-coupling of aryl bromides with sodium azide enables the synthesis diarylamines and primary anilines under mild reaction conditions. The oxidative addition electron-rich low-valent Ni photochemical conditions is endothermic. Herein, we demonstrate a light-mediated electronically rich that yields diarylamines, while electron-deficient gives access to at room temperature.

Язык: Английский

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ESI‐MS‐Visualization of Cyanoarene Photocatalysts by Specific Supramolecular Interaction with Br‐Anion

Chemistry - Methods, Год журнала: 2025, Номер unknown

Опубликована: Фев. 7, 2025

Abstract Isophthalonitrile derivatives (IPNs) have emerged as promising organic photocatalysts due to their efficiency and accessibility; however, inherent lability under light‐induced conditions poses significant challenges in monitoring transformation pathways. Understanding these pathways is crucial for optimizing photocatalytic processes enhancing reaction efficiency. In this study, we present a novel approach utilizing electrospray ionization mass spectrometry (ESI‐MS) visualize cyanoarene by taking advantage of specific supramolecular interaction with bromide anions. Our findings reveal that ions facilitate the detection IPNs products high sensitivity selectivity, even complex environments. The predominantly occurs gas phase, minimizing interference solution‐based transformations. developed anion‐enhanced (AED‐ESI‐MS) not only provides real‐time insights into photocatalyst behavior but also opens new possibilities detailed mechanistic investigation light‐driven reactions. proposed AED‐ESI‐MS using other anions may offer broad applicability be worth studying further across various systems.

Язык: Английский

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Illuminating Palladium Catalysis

Accounts of Chemical Research, Год журнала: 2025, Номер unknown

Опубликована: Фев. 26, 2025

ConspectusThe past decade has witnessed significant advancements of visible-light-induced photocatalysis, establishing it as a powerful and versatile tool in organic synthesis. The major focus this field centered on the development methodologies that either rely solely photocatalysts or combine photocatalysis with other catalytic methods, such transition metal catalysis, to address broader more diverse array transformations. Within rapidly evolving area, subfield we refer garnered attention due its growing impact mechanistic uniqueness. A distinguishing feature is dual functionality single complex, which not only acts photocatalyst initiate photochemical processes but also functions traditional catalyst, facilitating key bond-breaking bond-forming events. As such, an exogenous required photocatalysis. However, implications harnessing both excited- ground-state reactivities complex can extend beyond simplification. One most compelling aspects area photoexcited complexes exhibit unique inaccessible through conventional thermal photocatalytic approaches. These distinct be leveraged accomplish novel transformations by engaging entirely different substrate pool unlocking new known substrates.In 2016, our group pioneered use phosphine-ligated palladium catalysts upon visible-light irradiation engage substrates radical reactions. In initial discovery, showed photoexcitation redirect well-established oxidative addition Pd(0) into aryl iodides toward unprecedented process, generating hybrid Pd(I) species. We subsequently extended strategy formation alkyl radicals from halides. reactive intermediates have been harnessed wide variety transformations, including desaturation, Heck reactions, alkene difunctionalization cascades, among others.Seeking further expand avenue, achieved first example asymmetric context allylic C–H amination, where catalyst now plays triple duty additionally controlling stereochemical outcome reaction. parallel reaction established diazo compounds, strained molecules, electron-deficient alkenes serve precursors halides redox-active esters. Notably, engagement made possible photoinduced hydricity enhancement Pd–H species, representing mode reactivity.This Account presents discovery organized type explored. Given rapid progress field, anticipate will provide readers guiding principles inspiration for designing developing efficient

Язык: Английский

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Halogen Bonding Initiated Difunctionalization of [1.1.1]Propellane via Photoinduced Polarity Match Additions

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(51)

Опубликована: Авг. 28, 2024

Abstract Bicyclo[1.1.1]pentane (BCP), recognized as a bioisostere for para ‐disubstituted benzene, has gained widespread interest in drug development due to its ability enhance the physicochemical properties of pharmaceuticals. In this work, we introduce photoinduced, halogen bonding‐initiated, metal‐free strategy synthesizing various BCP derivatives. This method involves generation nucleophilic α‐aminoalkyl radicals via halogen‐bonding adducts. These undergo selective radical addition [1.1.1]propellane, yielding electrophilic that subsequently participate polarity‐matched additions, culminating difunctionalization bicyclopentane. The versatility and practicality approach are underscored by broad substrate scope, which includes late‐stage functionalization series valuable transformations, all conducted under mild reaction conditions.

Язык: Английский

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Photoinduced Palladium-Catalyzed Radical Germylative Arylation of Alkenes with Chlorogermanes

The Journal of Organic Chemistry, Год журнала: 2024, Номер 89(17), С. 12848 - 12852

Опубликована: Авг. 15, 2024

We describe a visible light-induced palladium-catalyzed radical germylative arylation of alkenes with easily accessible chlorogermanes. This protocol provides expedient access to germanium-substituted indolin-2-ones in good excellent yields under mild reaction conditions. The key step for this strategy lies the reductive activation germanium–chloride bonds an excited palladium complex light irradiation. involvement germanium radicals was evidenced by electron paramagnetic resonance spectroscopy experiments.

Язык: Английский

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An Efficient Supported Cu(I) Catalyst for the Amination of Aryl Halides with Sodium Azide

ChemNanoMat, Год журнала: 2024, Номер 10(6)

Опубликована: Март 27, 2024

Abstract We present the synthesis and characterization of a new Cu(I) complex supported on SBA‐15 as catalyst for preparing anilines from reaction aryl halides with sodium azide. The support was modified by treating it sequentially (3‐aminopropyl) triethoxysilane (APTES), cyanuric chloride, 2‐aminothiazole (AT). mesoporous silica, SBA‐15@BAT, then treated CuI solution in acetonitrile to give SBA‐15@BAT‐Cu(I). underwent thorough using conventional methods. X‐Ray photoelectron spectroscopy (XPS) analysis corroborated presence copper +1 oxidation state catalyst. sufficiently catalyzed amination iodo‐, bromo‐, chloroarenes NaN 3 . centrifuged, washed, applied subsequent run. investigated effects various components parameters determine optimal conditions reaction. heterogeneous exhibited noticeable stability reused over seven runs slight deactivation.

Язык: Английский

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Transition-Metal-Catalyzed Direct Arylation of Ammonia

Synthesis, Год журнала: 2024, Номер 56(19), С. 2963 - 2972

Опубликована: Апрель 16, 2024

Abstract In the past few decades, transition-metal-catalyzed direct amination of aryl halides with ammonia has attracted significant attention from chemists because its broad substrate scope, good functional group compatibility, and high reaction selectivity. Herein, recent examples syntheses aniline derivatives starting are reviewed. 1 Introduction 2 Heat-Driven Transition-Metal-Catalyzed Amination Aryl Electrophiles 2.1 Palladium-Catalyzed 2.2 Copper-Catalyzed 2.3 Nickel-Catalyzed 3 Light-Driven 4 Conclusion Outlook

Язык: Английский

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Catalysed Aryl Amine Syntheses via Azides: From Azidation of Aryl Halides to Azide Reduction and Direct Amination

ChemCatChem, Год журнала: 2024, Номер unknown

Опубликована: Май 6, 2024

Abstract This review summarises and discusses aryl amine azide syntheses from halides employing azides. The majority of the reported reactions proceed with copper catalysis or mediation. Often, an is formed in first step, which then reduced situ to a second step. occurrence reduction, depends on chosen reaction conditions substrates. formation only azides through Cu‐mediated C−N bond formations discussed, followed by mediated catalytic reduction different systems, azidation amines, viz . azidation‐amination strategies. allows for synthesis complex heterocycles multi‐step one‐pot procedures, several are summarised here. Examples application synthesising important amines employed as biologically active compounds, materials science also summarised. Finally, conducted control have been collected discussed combination mechanistic proposals. literature survey us pinpoint design criteria valuable includes choice such solvent system additives, involved metal promising

Язык: Английский

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Visible Light‐Promoted Mono‐Bromination of Aniline Derivatives and Nitrogen‐Containing Heterocyclic Compounds via Electron Donor−Acceptor Complex

Asian Journal of Organic Chemistry, Год журнала: 2024, Номер unknown

Опубликована: Июнь 11, 2024

Abstract We present a successful development of photo‐induced mono‐bromination method for anilines, which eliminates the requirement photocatalysts and excess bromine sources. Experimental investigations, complemented by computational analyses, establish that this operates via formation an electron donor‐acceptor (EDA) complex. This innovative approach enables synthesis highly regioselective mono‐brominated products across diverse range substrates, all achieved under mild reaction conditions.

Язык: Английский

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