Transition Metal‐Catalyzed Direct Functionalization of Carbazoles

The Chemical Record, Journal Year: 2025, Volume and Issue: unknown

Published: April 29, 2025

Abstract Carbazoles are an important class of nitrogen‐containing heterocycles found in diverse natural products, bioactive molecules, and functional materials. Their broader applications have driven extensive research into their synthesis functionalization. Among various approaches, transition metal‐catalyzed C−H activation has emerged as a powerful tool for direct functionalization, offering regioselectivity, efficiency, sustainability. This review comprehensively summarizes advancements functionalization carbazoles. Various catalytic systems employing palladium, ruthenium, rhodium, nickel, cobalt, copper, iron enabled alkylation, alkenylation, acylation, arylation, alkynylation, heteroatom incorporation These methodologies late‐stage diversification opened avenues accessing structurally complex carbazole derivatives with tailored properties. The aims to provide comprehensive guide researchers exploring via activation, highlighting key mechanistic insights, scope, emerging trends this field.

Language: Английский

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Photoredox Radical Cascade Cyclization of 2‐Alkynylarylnitriles in Visible Light: Direct Access to 3‐Amino‐1‐indenones

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: 366(9), P. 2072 - 2078

Published: March 1, 2024

Abstract A photoinduced direct synthesis of 3‐amino‐1‐indenones via radical cascade cyclization strategy is demonstrated. The methodology involves a domino reaction between 2‐alkynylarylnitrile and N ‐aminopyridinium salt captures the reactivity in‐situ generated nitrogen‐centered (NCR) in visible light. Multiple bond‐forming events including C−N, C−C, C−O take place sequentially on enabling construction 3‐amino‐1‐indenone core at room temperature 35–76% yield. preliminary biological screening synthesized compounds indicative their potent anti‐cancer property.

Language: Английский

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Dual Palladium-Photoredox-Mediated Regioselective Acylation of Carbazoles and Indolines

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(19), P. 13686 - 13698

Published: Sept. 28, 2023

We have described a dual palladium-photoredox-catalyzed highly regioselective acylation of carbazoles and indolines using molecular oxygen as the green oxidant. The reaction shows broad substrate scope good functional group tolerance. Late-stage functionalization carprofen drug derivative, further manipulation products, gram-scale synthesis acylated products were illustrated to show versatility method.

Language: Английский

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Substituent-controlled regioselective arylation of carbazoles using dual catalysis

Organic & Biomolecular Chemistry, Journal Year: 2023, Volume and Issue: 22(4), P. 753 - 758

Published: Dec. 20, 2023

Controlled regioselective mono- and di-arylation of carbazoles using dual palladium–photoredox catalysis.

Language: Английский

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Visible‐Light Induced Ag‐Palladacycle‐Complex‐Mediated Regioselective C−H Arylation

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: 366(17), P. 3603 - 3609

Published: June 20, 2024

Abstract A visible‐light‐induced, external photocatalyst‐free, site‐selective C−H arylation of 4 H ‐pyrido[1,2‐ a ]pyrimidin‐4‐ones and various 2‐aryl heteroarenes has been developed to provide ortho arylated products 41–95% yield at room temperature. mechanistic study using control experiments, UV‐visible study, DFT observation colored aggregates suggest that in situ generated Ag‐palladacycle complex is responsible for absorbing the visible light generating aryl radicals from aryldiazonium salts. Further, this methodology demonstrates its versatility by transforming heteroarenes, including 2‐phenylquinazolin‐4(3 )‐one, 3‐phenylquinoxalin‐2(1 2‐phenylpyridines, pyrazolo[1,5‐ ]pyrimidines, 2‐phenylquinolines, 2‐phenylisoquinolines, 2‐phenylbenzo[ d ]thiazoles, into their respective regio‐selective under mild reaction conditions.

Language: Английский

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Raman Monitoring of the Electro-Optical Synergy-Induced Enhancements in Carbon–Bromine Bond Cleavage, Reaction Rate, and Product Selectivity of p-Bromothiophenol

ACS Applied Materials & Interfaces, Journal Year: 2024, Volume and Issue: 16(21), P. 27831 - 27840

Published: May 17, 2024

Electro-optical synergy has recently been targeted to improve the separation of hot carriers and thereby further efficiency plasmon-mediated chemical reactions (PMCRs). However, electro-optical in PMCRs needs be more deeply understood, its contribution bond dissociation product selectivity clarified. Herein, reduction p-bromothiophenol (PBTP) was studied on a plasmonic nanostructured silver electrode using situ Raman spectroscopy theoretical calculations. It found that synergy-induced enhancements cleavage carbon-bromine bonds, reaction rate, (4,4'-biphenyl dithiol vs thiophenol) were largely affected by applied bias, laser wavelength, power. The simulation clarified strong is attributed matching energy band diagrams with those adsorbed PBTP molecules. A deep understanding clarification mechanism will highly beneficial for development other efficient PMCRs.

Language: Английский

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Palladium‐Catalyzed Direct Alkynylation of Carbazoles with Alkynyl Bromides

European Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 27(40)

Published: June 18, 2024

Abstract Carbazole derivatives are vital in medicinal and materials chemistry, yet accessing diverse substitutions remains challenging. Here, we introduce a regioselective approach for C1 C8 alkynylation of carbazoles via palladium‐catalyzed C−H activation. This method provides direct route to mono‐ di‐alkynylated derivatives, addressing the scarcity alkynylated carbazole‐based materials. Our study broadens synthetic toolbox carbazole functionalization, offering potential applications optoelectronics, bio‐imaging, beyond, while contributing developing sustainable activation methodologies.

Language: Английский

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Green light-mediated dual eosin Y/Pd^II-catalyzed C(sp²)–H arylation of N–H unprotected 2-arylquinazolinones

Organic & Biomolecular Chemistry, Journal Year: 2024, Volume and Issue: 22(27), P. 5540 - 5545

Published: Jan. 1, 2024

An eosin Y/Pd II dual catalytic highly regio- and chemoselective C(sp 2 )–H monoarylation of N–H unprotected 2-phenyl quinazolinones with diazonium salts under visible light irradiation is disclosed.

Language: Английский

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Visible-Light-Driven Regioselective Decarboxylative Acylation of N-Methyl-3-phenylquinoxalin-2(1H)-one by Dual Palladium–Photoredox Catalysis Through C–H Activation

ACS Omega, Journal Year: 2023, Volume and Issue: 9(1), P. 651 - 657

Published: Dec. 16, 2023

We report herein an efficient visible-light-promoted approach for the regioselective decarboxylative C–H acylation of N-methyl-3-phenylquinoxalin-2(1H)-ones using α-oxo-2-phenylacetic acids via dual palladium–photoredox catalysis. The reactions were carried out at room temperature in presence 24 W blue LEDs. established protocol tolerated a wide range functional groups and enabled synthesis several acylated good to excellent yields. proposed mechanism this transformation was supported by control experiments.

Language: Английский

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Uses of Palladium Complexes in Accelerating Chemical Reactions under Visible Light Irradiation

Journal of Transition Metal Complexes, Journal Year: 2024, Volume and Issue: 7, P. 1 - 8

Published: Jan. 1, 2024

Language: Английский

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