Recent Advances in the Catalytic Synthesis of α‐Ketoamides

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

Published: April 21, 2025

Abstract α ‐Ketoamides are privileged chemical entities featuring a carbonyl group bonded to an amide. Bearing two pronucleophilic and proelectrophilic sites, this structural scaffold exhibits distinct properties unparalleled biological activity. Owing its wide application in medicinal, agricultural, synthetic chemistry, methods for assembling moiety ever‐growing demand. With the increasing focus on green synthesis, traditional routes ‐ketoamides have faded recent years giving rise development of photocatalytic, electrosynthetic, microwave‐assisted catalytic protocols. We hereby provide comprehensive critical summary all advancements witnessed field from 2016 present.

Language: Английский

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Microwave-assisted chemoselective transamidation of secondary amides by selective N–C(O) bond cleavage under catalyst, additive and solvent-free conditions

Chemical Communications, Journal Year: 2023, Volume and Issue: 59(94), P. 14009 - 14012

Published: Jan. 1, 2023

An efficient environmentally friendly microwave-assisted approach under catalyst, additive and solvent-free conditions for the N -Boc-activated secondary amide transamidation via tetrahedral intermediate was developed.

Language: Английский

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Reductive cross-coupling of N-acyl pyrazole and nitroarene using tetrahydroxydiboron: synthesis of secondary amides

Organic & Biomolecular Chemistry, Journal Year: 2023, Volume and Issue: 21(41), P. 8329 - 8334

Published: Jan. 1, 2023

We report on a new method for the synthesis of amides using acyl pyrazoles and nitroarenes under reducing conditions. It was found that react with organo-nitro compounds in presence B2(OH)4, giving corresponding good yields. demonstrated benzoyl having various substituents different can be used to produce range N-substituted benzamides. The shows functional group tolerance has potential application variety organic molecules.

Language: Английский

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De Novo Synthesis of α‐Ketoamides via Pd/TBD Synergistic Catalysis

Advanced Science, Journal Year: 2024, Volume and Issue: unknown

Published: July 10, 2024

Precisely controlling the product selectivity of a reaction is an important objective in organic synthesis. α-Ketoamides are vital intermediates chemical transformations and privileged motifs numerous drugs, natural products, biologically active molecules. The selective synthesis α-ketoamides from feedstock chemicals safe operationally simple manner under mild conditions long-standing catalysis challenge. Herein, unprecedented TBD-switched Pd-catalyzed double isocyanide insertion for assembling ketoamides aqueous DMSO (hetero)aryl halides pseudohalides reported. effectiveness utility this protocol demonstrated by its diverse substrate scope (93 examples), ability to late-stage modify pharmaceuticals, scalability large-scale synthesis, pharmaceutically Mechanistic studies indicate that TBD key ligand modulates process, thereby selectively providing desired unique manner. In addition, imidoylpalladium(II) complex α-ketoimine amide successfully isolated determined X-ray analysis, confirming they probable catalytic pathway.

Language: Английский

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Photocatalytic Decarboxylative Cross-Coupling of α,β-Unsaturated Acids with Amines for α-Ketoamides via C–N Bond Formation

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(22), P. 16750 - 16758

Published: Nov. 5, 2024

An unprecedented oxidative decarboxylative chemical domain of α,β-unsaturated acids and amines for C-N cross-coupled α-ketoamidation is disclosed. Molecular oxygen as a source in amide water the ketone segment furnished green sustainable synthesis α-ketoamide from feedstock amines. Mechanistically, photocatalyst travels with reductive quenching cycle, whereas pallado-cycle proceeded through bond formation. Broad substrate scope, functional group tolerance, CO

Language: Английский

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Visible‐Light‐Mediated Synthesis of α‐Ketoamides via Oxidative Amination of 2‐Bromoacetophenones Using Eosin Y as a Photoredox Catalyst

Chemistry - An Asian Journal, Journal Year: 2023, Volume and Issue: 18(19)

Published: Aug. 29, 2023

An oxidative amination of 2-bromoacetophenones has been accomplished to provide α-ketoamides by using photoredox catalysis with air as oxidant. The reactants are readily accessible, and the method is endowed broad substrate scope good functional group tolerance. practicality approach also shown a gram-scale reaction.

Language: Английский

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Molecular Oxygen‐Induced Transamidation of Unactivated Amides in Diethyl Carbonate in the Presence of a Palladium Catalyst

Advanced Synthesis & Catalysis, Journal Year: 2023, Volume and Issue: 365(24), P. 4713 - 4725

Published: Nov. 9, 2023

Abstract Herein we disclose a palladium‐catalyzed procedure for the transamidation of structurally diverse amides with amines based on use molecular oxygen as palladium‐activating agent. The reaction, which is scalable and amenable preparation enantioenriched compounds, carried out in bio‐degradable solvent often used fuel additive, diethyl carbonate. As result 10 −4 mol% catalyst required, final products are isolated containing palladium impurities concentration 0.1 ppm. Two kinetically different mechanistic pathways proposed this reaction account number experiments such kinetic curves, TEM images, poisoning experiments, UPLC‐ESI‐MS identification intermediates EPR spectra crude.

Language: Английский

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CuBr2/1,10-phenanthroline-catalyzed benzylic oxidation via a bromo intermediate for the synthesis of α-keto esters under continuous-flow conditions

Molecular Catalysis, Journal Year: 2024, Volume and Issue: 566, P. 114409 - 114409

Published: Aug. 2, 2024

Language: Английский

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De Novo Synthesis of α-Ketoamides via Pd/TBD Synergistic Catalysis

Research Square (Research Square), Journal Year: 2024, Volume and Issue: unknown

Published: April 19, 2024

Abstract Precise control on the product selectivity of a reaction is an important objective in organic synthesis. α-ketoamides are vital intermediates chemical transformation and privileged motifs numerous drugs, natural products biologically active molecules. The selective synthesis from feedstock chemicals safe operationally simple manner under mild conditions long-standing challenge catalysis. Herein we disclose unprecedented TBD-switched Pd-catalyzed double isocyanide insertion (hetero)aryl halides or pseudohalides for assembly aqueous DMSO conditions. effectiveness utility this protocol demonstrated by diverse substrate scope (85 examples), late-stage modification pharmaceuticals, scalability large-scale synthesis, transformations functional groups, as well pharmaceutically Mechanistic studies indicate that TBD key ligand to modulate process, thus selectively providing desired unique manner. In addition, imidoylpalladium(II) complex α-ketoimine amide successfully isolated determined X-ray analysis, proving them probable catalytic pathway.

Language: Английский

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Heterogeneous Catalytic Aerobic Oxidation of Primary Amines to Amides Using Unsupported Nanoporous Palladium Catalyst

Journal of Organometallic Chemistry, Journal Year: 2024, Volume and Issue: 1014, P. 123189 - 123189

Published: May 20, 2024

Language: Английский

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