Contemporary Approaches for Amide Bond Formation

Advanced Synthesis & Catalysis, Journal Year: 2023, Volume and Issue: 365(24), P. 4359 - 4391

Published: Nov. 7, 2023

Abstract Amide bond construction has garnered significant interest in recent decades due to amides being one of the most prevalent functional groups among bioactive molecules. Out thirty‐seven new drugs approved by FDA 2022, eleven are small molecules containing at least amide bond. Additionally, there nineteen large as drugs, some which have peptide structures, and therefore, also bear bonds. In years, multiple teams embraced challenge developing more efficient methods for formation. This dedication led numerous publications appearing monthly prestigious journals, showcasing advancements this field. The primary goal review is present viable strategies constructing It crucial differentiate between formation synthesis; hence, focus on describing specific forming C(O)−N particular, concentrates developed within last six years. There a particular emphasis approaches that consider thought process when selecting starting materials groups. approach ensures coverage all common chemical transformations yield

Language: Английский

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Nickel-Catalyzed Modular Four-Component 1,4-Alkylcarbonylation of 1,3-Enynes to Tetra-Substituted CF₃–Allenyl Ketones

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(4), P. 2144 - 2150

Published: Jan. 25, 2024

The modular four-component carbonylation of unsaturated hydrocarbons represents an elegant strategy for the one-pot synthesis complex carbonyl compounds. However, this is currently focused on 1,2-difunctionalization olefins or alkynes, and 1,4-alkylcarbonylation 1,3-enynes remains unexplored. In study, we report a Ni-catalyzed CF3-containing under 1 atm CO, which affords tetra-substituted CF3-allenyl ketones with good yields selectivity. This protocol features mild conditions, broad substrate scope, acceptable functional group compatibility. Control experiments revealed that reactivity oxime esters (regulated by leaving groups) polarity matching are crucial success cascade. Preliminary mechanistic studies suggest acyl nickel key intermediate in transformation.

Language: Английский

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Palladium-Catalyzed Carbonylations: Application in Complex Natural Product Total Synthesis and Recent Developments

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(8), P. 4925 - 4941

Published: Jan. 27, 2023

Carbon monoxide is a cheap and abundant C1 building block that can be readily incorporated into organic molecules to rapidly build structural complexity. In this Perspective, we outline several recent (since 2015) examples of palladium-catalyzed carbonylations in streamlining complex natural product total synthesis highlight the strategic importance these carbonylation reactions corresponding synthesis. The selected include spinosyn A, callyspongiolide, perseanol, schizozygane alkaloids, cephanolides, bisdehydroneostemoninine related stemona alkaloids. We also provide our perspective about advancements future developments carbonylations.

Language: Английский

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Nickel-Catalyzed Multicomponent Carbodifluoroalkylation of Electron-Deficient Alkenes

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(7), P. 4111 - 4119

Published: March 10, 2023

The nickel-catalyzed multicomponent dicarbofunctionalization of alkenes represents one the most straightforward approaches to complex organofluorine compounds. However, catalytic carbofluoroalkylation electron-deficient remains underdeveloped. Here, we report a three-component aryldifluoroalkylation industry-relevant acrylonitrile and acrylate with arylboronic acids difluoroalkyl halides. reaction can extend four-component carbonylation under 1 atm CO gas. This modular synthesis features synthetic convenience, high functional group tolerance, simple components construct difluoroalkylated compounds expediently. utility has also been demonstrated by diversified transformations resulting products into medicinal interest fluorinated

Language: Английский

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Nickel-Catalyzed Carbonylative Negishi Cross-Coupling of Unactivated Secondary Alkyl Electrophiles with 1 atm CO Gas

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(12), P. 7971 - 7978

Published: March 14, 2024

We describe a nickel-catalyzed carbonylative cross-coupling of unactivated secondary alkyl electrophiles with the organozinc reagent at atmospheric CO gas, thus allowing expedient construction unsymmetric dialkyl ketones broad functional group tolerance. The leverage newly developed

Language: Английский

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Modular assembly of arenes, ethylene and heteroarenes for the synthesis of 1,2-arylheteroaryl ethanes

Nature Chemistry, Journal Year: 2024, Volume and Issue: 16(10), P. 1705 - 1714

Published: June 27, 2024

Language: Английский

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Nickel-Catalyzed Hydrocarbamoylation of Alkenes with Isocyanates

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: March 17, 2025

The hydrocarbamoylation of alkenes with isocyanates is a promising method for synthesizing amides. However, applying this strategy to more inert, simple alkenes, such as styrenes, α-olefins, and internal poses significant challenges. Here, we report the first nickel-catalyzed isocyanates, facilitated by triethoxysilane reduce nickelacycle intermediates. By switching ligands─including 6,6′-dimethyl-2,2′-bipyridine N-heterocyclic carbene─this efficiently produces amides from diverse array including gaseous olefins.

Language: Английский

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Recent Advances in Nickel Catalyzed Carbonylative Reactions via the Insertion of Carbon Monoxide^†

Chinese Journal of Chemistry, Journal Year: 2023, Volume and Issue: 42(2), P. 177 - 189

Published: Sept. 4, 2023

Comprehensive Summary Carbonyl compounds have attracted considerable attention due to their extensive applications in drug discovery. Furthermore, they are important synthetic intermediates for the construction of carbon‐carbon and carbon‐heteroatom bonds. Transition‐metal‐catalyzed carbonylation via insertion CO is one most efficient straightforward strategies access carbonyl compounds. However, transition‐metal‐catalyzed carbonylative reactions require expensive toxic noble‐metal catalysts. Therefore, there a growing demand exploration nickel‐catalyzed earth abundance low cost nickel. Compared with well‐established palladium‐catalyzed reactions, analogous transformations been relatively underdeveloped. This primarily because strongly binds nickel, often resulting catalyst poisoning. In recent years, some research groups focused on using surrogates or NN 2 pincer nickel circumvent formation Ni(CO) 4 . Nickel‐catalyzed has applied carbonyl‐containing compounds, such as ketones, carboxylic acids, thioesters, acyl chloride carboxamides.

Language: Английский

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Manganese-Catalyzed Carbonylation of Unactivated Alkyl Bromides with Alkylidenecyclopropanes

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(12), P. 9487 - 9495

Published: June 7, 2024

Language: Английский

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Palladium-Catalyzed Cascade Carbonylation Reaction To Construct Ester Derivatives

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: March 24, 2025

We have developed a palladium-catalyzed ester carbonylation reaction that enables the synthesis of ester-substituted benzofuran derivatives in single step through introduction alkyl halides undergoing situ hydrolysis and alkynyl aryl iodides. This method demonstrates broad applicability to both primary secondary while maintaining excellent functional group compatibility under low palladium loading conditions. Notably, this strategy significantly expands scope reactions.

Language: Английский

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