Mechanistic Investigations of Cobalt-Catalyzed, Aminoquinoline-Directed C(sp²)–H Bond Functionalization

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

Published: Jan. 10, 2025

Monoanionic, bidentate-auxiliary-directed, cobalt-catalyzed C–H bond functionalization has become a very useful tool in organic synthesis. A comprehensive investigation into isolated organometallic intermediates and their reactivity within the catalytic cycle is lacking. We report here mechanistic studies of cobalt-catalyzed, aminoquinoline-directed C(sp2)–H functionalization. number Co(III) have been structurally characterized, including, for first time aminoquinoline system, complexes arising from migratory insertion cobalt–carbon bonds. The stoichiometric reactions cobalt(III) aryls with alkenes, alkynes, carbon monoxide, cyclic secondary amines, benzamides explored. oxidation state cobalt product-forming step depends on nature coupling component. Specifically, annulation alkynes carbonylation CO likely proceed via Co(I)/Co(III) cycle. Carbon–hydrogen alkenes as well benzamide homocoupling, (formally) Co(IV) species involve oxidatively induced reductive elimination.

Language: Английский

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Late‐Stage C−H Activation of Drug (Derivative) Molecules with Pd(ll) Catalysis

Chemistry - A European Journal, Journal Year: 2023, Volume and Issue: 29(71)

Published: Oct. 17, 2023

Abstract This review comprehensively analyses representative examples of Pd(II)‐catalyzed late‐stage C−H activation reactions and demonstrates their efficacy in converting bonds at multiple positions within drug (derivative) molecules into diverse functional groups. These transformative hold immense potential medicinal chemistry, enabling the efficient selective functionalization specific sites molecules, thereby enhancing pharmacological activity expanding scope candidates. Although notable articles have focused on drug‐like using transition‐metal catalysts, reviews specifically focusing Pd(II) catalysts are required owing to prominence as most widely utilized metal for ability introduce a myriad groups bonds. The utilization Pd‐catalyzed methodologies impressive success introducing various groups, such cyano (CN), fluorine (F), chlorine (Cl), aromatic rings, olefin, alkyl, alkyne, hydroxyl with high regioselectivity functional‐group tolerance. breakthroughs serve invaluable tools discovery development, offering strategic options optimize candidates drive exploration innovative therapeutic solutions.

Language: Английский

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Copper‐Catalyzed Fluoroamide‐Directed Remote C(sp³)‐H Bond Functionalization Through Intramolecular Hydrogen Atom Transfer

European Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 27(13)

Published: Feb. 15, 2024

Abstract Direct C−H functionalization is an important strategy for the rapid synthesis of valuable organic molecules. Radical‐involved remote C(sp 3 )‐H based on hydrogen atom transfer (HAT) becomes method enabling selective direct transformation bonds at specific distal position(s). In recent years, copper‐catalyzed fluoroamide‐directed bond through intramolecular HAT has served as a robust and elegant assembly variety functionalized (sulfon)amides related derivatives. This review focuses advances in this area. These transformations proceed effectively with high selectivities good functional group compatibility under mild conditions.

Language: Английский

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Transition‐Metal‐Catalyzed Directed C−H Functionalization in/on Water

Chemistry - An Asian Journal, Journal Year: 2023, Volume and Issue: 19(1)

Published: Nov. 6, 2023

Abstract Directing group assisted C−H bond functionalization using transition‐metal‐catalysis has emerged as a reliable synthetic tool for the construction of regioselective carbon‐carbon/heteroatom bonds. Off late, “in/on water directed transition‐metal‐catalysis”, though still underdeveloped, appeared one prominent themes in sustainable organic chemistry. This article covers advancements, mechanistic insights and application (hetero)arenes in/on presence transition‐metal‐catalysis.

Language: Английский

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Pd(II)-Catalyzed, Picolinamide-Aided γ-(sp2)-C–H Functionalization of Racemic and Enantiopure α-Methylbenzylamine and Phenylglycinol Scaffolds

Synthesis, Journal Year: 2022, Volume and Issue: 54(18), P. 4059 - 4094

Published: April 20, 2022

Abstract In this paper, we report the Pd(II)-catalyzed, picolinamide DG-aided sp2 γ-C–H functionalization and expansion of library enantiopure α-methylbenzylamine phenylglycinol scaffolds. We have shown synthesis a wide range racemic ortho-C–H arylated, alkylated, brominated, iodinated Various R S (chiral) functionalized scaffolds were synthesized with good enantiopurities. Racemic derivatives are important building blocks in organic medicinal chemistry. Accordingly, work contributes to libraries motifs substrate scope development through Pd(II)-catalyzed bidentate directing group picolinamide-aided site-selective C–H activation method.

Language: Английский

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Dual Metallaphotoredox‐Catalyzed Directed C(sp²)−H Functionalization: Access to C−C/C‐Heteroatom Bonds

European Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 2022(39)

Published: June 22, 2022

Abstract Metallaphotoredox catalysis represents the combination of two activation modes: metal‐catalyzed C−H functionalization and visible‐light‐induced photocatalysis. This appealing dual technique has evolved as a versatile platform that paved way for diverse low‐energy pathways plethora synthetic transformations. The synergistic “green” approaches garnered enormous interest owing to development sustainable strategies. In recent past, significant advancements have been accomplished in constructing site‐selective C−C C‐heteroatom bonds. review outlines use photoredox directing group‐assisted reactions. mechanistic insights developments applications are addressed.

Language: Английский

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Azobenzene-based unnatural amino acid scaffolds via a Pd(ii)-catalyzed C(sp³)–H arylation strategy

Chemical Communications, Journal Year: 2022, Volume and Issue: 58(93), P. 12967 - 12970

Published: Jan. 1, 2022

Azobenzene-based unnatural amino acid motifs were constructed via the Pd( ii )-catalyzed diastereoselective β-C(sp 3 )–H arylation and Mills azo coupling tactics.

Language: Английский

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Pd(II)-Catalyzed Directing-Group-Aided C–H Arylation, Alkylation, Benzylation, and Methoxylation of Carbazole-3-carboxamides toward C2,C3,C4-Functionalized Carbazoles

Synthesis, Journal Year: 2023, Volume and Issue: 55(21), P. 3535 - 3567

Published: March 16, 2023

Abstract We report the Pd(II)-catalyzed β-C–H arylation, alkylation, benzylation, and methoxylation of carbazole-3-carboxamide carbazole-2-carboxamide substrates, assisted by bidentate directing groups 8-aminoquinoline or 2-(methylthio)aniline, construction C2,C3,C4-functionalized carbazole motifs. The arylation reaction was attempted using different such as 8-aminoquinoline, 4-amino-2,1,3-benzothiadiazole, 4-methoxyquinolin-8-amine, butan-1-amine. Through optimization reactions, 2-(methylthio)aniline were found to be suitable and, especially, an efficient group in carbazole-3-carboxamide, substrates. An ample number arylated, alkylated, benzylated, methoxylated carbazole-3-carboxamides synthesized. structures representative β-C(2)–H arylated motifs unequivocally confirmed single-crystal X-ray structure analysis. Given wide range applications carbazoles chemistry, materials sciences, medicinal chemistry there have been constant efforts for developing new methods synthesizing functionalized carbazoles. This work contributes expansion library through a directing-group-aided site-selective activation functionalization carbazole-3-carboxamides.

Language: Английский

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Transition‐Metal‐Catalyzed Remote C(sp³)−H Functionalization Of Carboxylic Acid And Its Derivatives

Asian Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 11(7)

Published: May 31, 2022

Abstract Carboxylic acids are ubiquitous functional groups present in many bio‐relevant molecules, including drugs and amino acids. In general, α‐ β−C(sp 3 )−H bonds of carboxylic easy to functionalize, contrary remote (γ‐ δ) C−H which difficult due the distal location these from group. On other hand, functionalizing an inert C(sp bond is another critical challenge synthetic chemistry its lower acidity reactivity. Nevertheless, last decade has witnessed tremendous development sp ‐C−H functionalization acid derivatives. Here, this review, we have delineated recent progress γ‐ δ‐C−H aliphatic acids/amino their This review further subdivided based on type reaction. Finally, presented some applications methodologies, such as total synthesis hibispeptin A, etc.

Language: Английский

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Expedient Ni-catalyzed C–H/C–H cross-dehydrogenative coupling of aryl amides with azoles

Chemical Communications, Journal Year: 2022, Volume and Issue: 58(40), P. 5980 - 5983

Published: Jan. 1, 2022

A nickel-catalyzed C-H heteroarylation of arenes has been described using a removable oxazoline-aniline derived directing group. Utilization an inexpensive nickel(II)-catalyst, substrate scope, functional group diversity and late-stage functionalization xanthine-derived commercial drugs are the important practical features.

Language: Английский

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