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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Maleimide‐Controlled Formation of Indanonylpyrrolinediones and Spiroindanonylpyrrolinediones via Rh(III)‐Catalyzed C−H Activation of Sulfoxonium Ylides

Advanced Synthesis & Catalysis, Journal Year: 2023, Volume and Issue: 365(24), P. 4595 - 4602

Published: Nov. 1, 2023

Abstract A substrate‐controlled [4+1] annulation of sulfoxonium ylides with maleimides via Rh(III)‐catalyzed C−H bond activation is developed. The reaction 2‐methyl‐ N ‐arylmaleimides in the presence AgNTf 2 diastereoselectively provides diversely functionalized indanonylpyrroline‐2,5‐dione derivatives. Furthermore, AgBF 4 , subsequent leads to biologically intriguing various spiroindanonylpyrroline‐2,5‐diones. This methodology offers a broad substrate scope, good functional group tolerance, and diastereoselectivity.

Language: Английский

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Lithium Bromide-Promoted Formal C(sp³)–H Bond Insertion Reactions of β-Carbonyl Esters with Sulfoxonium Ylides to Synthesize 1,4-Dicarbonyl Compounds

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(10), P. 6974 - 6986

Published: May 4, 2024

A LiBr-promoted formal C(sp3)–H bond insertion reaction between β-carbonyl esters and sulfoxonium ylides is established. This practical has a wide range of substrate scope for both to give variety 1,4-dicarbonyl compounds with 43–94% yields. The features transition-metal-free conditions exclusive C-alkylation chemselectivity. use bench-stable overcomes previous methods that require transition metal as catalysts unstable diazo or toxic haloketones alkylation reagents.

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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Copper-Mediated Decarboxylative Coupling of 3-Indoleacetic Acids with Sulfoxonium Ylides for the Synthesis of α-Acetoxyl Ketones

Organic Letters, Journal Year: 2024, Volume and Issue: 26(28), P. 5940 - 5945

Published: July 11, 2024

The most convenient and direct method of synthesizing an α-acyloxy ketone is the reaction a diazo compound with carboxylic acid via O-H insertion. However, due to limitations in preparing storing compounds, application this restricted. In study, Cu(OAc)

Language: Английский

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Selective Synthesis of Amides and α-Ketoamides via Electrochemical Decarboxylation and Dehydration

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(15), P. 10498 - 10510

Published: July 16, 2024

An electrochemical and selective decarboxylation dehydration using α-keto acids with amines is accomplished, which leads to the easy accessibility of amides α-ketoamides, are not only ubiquitous valuable structure motifs found in pharmaceuticals, but also versatile building blocks synthetic chemistry. Notably, for this efficient green protocol, neither metal catalysts nor external oxidants required. The process exhibits a broad scope functional group tolerance deliver various α-ketoamides. Moreover, these two reactions have been applied late-stage derivatization can be safely conducted on gram scale.

Language: Английский

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Electrochemical Formation of α-Ketoamides from Ketoximes through Non-Beckmann Mechanism Pathway

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(9), P. 6238 - 6246

Published: April 23, 2024

α-Ketoamides are highly valued in synthetic chemistry due to their incorporation into diverse natural products and drug molecules. Here, we present an innovative electrochemical approach for constructing α-ketoamides, utilizing a mild environmentally friendly strategy user-friendly undivided cell setup under constant current. The excellent functional-group tolerance, convenient accessibility of reaction instruments starting materials, easy scalability collectively enhance the importance this protocol compared previous challenging methods. Additionally, mechanistic insight is obtained through investigation cyclic voltammograms reactants.

Language: Английский

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LiBr-Promoted Reaction of β-Ketodithioesters and Thioamides with Sulfoxonium Ylides to Synthesize Functionalized Thiophenes

Organic Letters, Journal Year: 2024, Volume and Issue: 26(43), P. 9401 - 9406

Published: Oct. 22, 2024

An operationally simple and highly efficient synthesis of functionalized thiophenes has been developed by LiBr promoted heteroannulation β-ketodithioesters thioamides with bench-stable sulfoxonium ylides in open air for the first time. This one-pot strategy involves formal Csp3–H bond insertion/intramolecular cyclization cascade, featuring readily accessible starting materials, TM additive-free condition, broad substrate scope, high functional group compatibility, scalability. Moreover, carbonyl, thiomethyl, amino groups resulting thiophene provide a good handle on downstream transformations.

Language: Английский

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Synthesis of N-Aryl-4-trifluoromethylthiazol-2-amines via Insertion/Annulation of Trifluoromethylimidoyl Sulfoxonium Ylides with Sodium Thiocyanate

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(17), P. 12255 - 12262

Published: Aug. 16, 2024

An efficient p-TsOH-mediated insertion of sodium thiocyanate into trifluoromethylimidoyl sulfoxonium ylides has been reported, affording annulated N-aryl-4-trifluoromethylthiazol-2-amines in 42–84% yields a one-pot manner. This protocol encompasses variety with serving as the source "S–C═N" moiety thiazole ring. The versatile transformations resulting pharmacologically important were also demonstrated.

Language: Английский

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Construction of α‐ketoamides via Photoredox‐Catalyzed N−H Insertion of Amines by Sulfoxonium Ylides

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 8, 2024

Abstract Herein, we report the development of photoredox‐catalyzed N−H insertion sulfoxonium ylides with amines via oxidative single‐electron transfer (SET). These reactions exhibit broad substrate scope (32 examples) and offer operationally simple, scalable procedures for accessing α ‐ketoamides in a single step. Mechanistic studies control experiments confirm participation photogenerated carbon radical facilitating (SET) from to initiate reaction.

Language: Английский

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