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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Switchable Radical Carbonylation by Philicity Regulation

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(32), P. 14923 - 14935

Published: Aug. 8, 2022

Carbonylation reactions involving CO as readily available C1 synthons have become one of the most important tools for construction carbonyl compounds from feedstock chemicals. Despite numerous catalytic methods carbonylation proceeding via ionic or radical pathways, an inherent limitation to these is need control switchable single and double carbonylative formation value-added products same simple starting materials. Here, we describe a new strategy that exploits photoredox catalysis regulate philicity amine coupling partners drive reactions. In carbonylation, amines were first transformed into nitrogen cations by single-electron transfer-oxidation coupled with form carbamoyl radicals, which further underwent cross-coupling incipient cyanoalkyl acyl radicals afford products. Upon addition stoichiometric 4-dimethylaminopyridine (DMAP), DMAP competitively traps initially formed relatively stabilized acyl-DMAP salts engaged in subsequent substitution nucleophilic produce The reaction proceeded smoothly excellent selectivity presence various nucleophiles at room temperature, generating valuable amides α-ketoamides versatile controlled fashion. Combined experimental computational studies provided mechanistic insights possible pathways.

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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Photoinduced Five‐Component Radical Relay Aminocarbonylation of Alkenes

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(41)

Published: Aug. 24, 2023

Radical single carbonylation reactions with CO constitute a direct and robust strategy toward various carbonyl compounds from readily available chemicals, have been extensively studied over the past decades. However, realizing highly selective catalytic systems for controlled radical double has remained substantial challenge, particularly more advanced multicomponent variants, despite their great potential value. Herein, we report visible-light-driven relay five-component aminocarbonylation reaction of unactivated alkenes using under metal-free conditions. This protocol provides access to valuable γ-trifluoromethyl α-ketoamides good yields high chemoselectivity. Crucial was identification distinct dual roles amine coupling partners, sequentially acting as electron donors formation photoactive donor-acceptor (EDA) complexes precursors then acceptor via nitrogen cations form carbamoyl radicals. Cross-coupling radicals acyl that are formed in an alkene-based process affords products.

Language: Английский

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Copper‐Catalyzed 1,2‐Dicarbonylative Cyclization of Alkenes with Alkyl Bromides via Radical Cascade Process

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(49)

Published: Oct. 18, 2022

Herein, we developed a new procedure on 1,2-dicarbonylative cyclization of 4-aryl-1-butenes with alkyl bromides. Using simple copper catalyst, two molecules carbon monoxide were introduced into the double bond formation four C-C bonds and ring. Various α-tetralones 2,3-dihydroquinolin-4-ones formed in moderate to good yields.

Language: Английский

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Constructing multiple active sites in iron oxide catalysts for improving carbonylation reactions

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: Aug. 17, 2023

Abstract Surface engineering is a promising strategy to improve the catalytic activities of heterogeneous catalysts. Nevertheless, few studies have been devoted investigate behavior differences multiple metal active sites triggered by surface imperfections on catalysis. Herein, oxygen vacancies induced Fe 2 O 3 catalyst are demonstrated with different around one vacancy and exhibited significant performance for carbonylation various aryl halides amines/alcohols CO. The developed system displays excellent activity, selectivity, reusability synthesis carbonylated chemicals, including drugs chiral molecules, via aminocarbonylation alkoxycarbonylation. Combined characterizations disclose formation vacancies. Control experiments density functional theory calculations demonstrate selective combination three vital catalyzing elemental steps PhI activation, CO insertion C-N/C-O coupling respectively, endowing combinatorial multistep reactions.

Language: Английский

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Recent Advances in Base‐Metal‐Catalyzed Carbonylation of Unactivated Alkyl Electrophiles^†

Chinese Journal of Chemistry, Journal Year: 2023, Volume and Issue: 41(23), P. 3419 - 3432

Published: July 27, 2023

Comprehensive Summary Transition metal‐catalyzed carbonylation reactions represent a direct and atom‐economical approach to synthesize carbonyl compounds or their derivatives by using CO as cheap readily available C1 feedstock. While of C(sp 2 )‐hybridized electrophiles ( e.g ., aryl halides) is well developed, less reactive unactivated alkyl remains challenging. Recently, the use earth‐abundant base metals including Cu, Co, Mn, Fe, Ni catalysts has enabled advances in carbonylative coupling for approaching diverse derivatives, notably, some which are synthetic importance but difficult be synthesized through previous reported methods. Herein, we have summarized discussed these recent achievements base‐metal‐catalyzed C—C, C—N, C—O, C—X other source.

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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Tuning the Oxidative Mono- or Double-Carbonylation of Alkanes with CO by Choosing a Co or Cu Catalyst

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(15), P. 9664 - 9669

Published: July 25, 2022

The control of reaction selectivity is a core organic synthesis, which requires the rational design catalytic system. Carbonylation reactions involving CO, such as monocarbonylation and double-carbonylation, are some most powerful tools for constructing carbonyl compounds. However, tunable mono- double-carbonylation still remain great challenge, especially C–H bonds. In this work, we introduced metal-controlled alkanes with amines to prepare alkyl amides α-ketoamides, respectively (58 examples, yields up 99%). Co catalysis system afforded solely products, Cu highly selective products (more than 20:1). Only choice or catalyst precursor was key producing dramatic switch in selectivity.

Language: Английский

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Palladium-Catalyzed Three-Component Cascade Carbonylation Reaction to Construct Benzofuran Derivatives

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(11), P. 7741 - 7746

Published: May 14, 2024

A novel three-component cyclization carbonylation reaction of iodoarene-tethered propargyl ethers with amine and CO is reported. This palladium-catalyzed cascade undergoes a sequence oxidative addition, unsaturated bond migration, carbonyl insertion, nucleophilic attack to deliver the benzofuran skeleton. Both aromatic amines aliphatic could proceed smoothly in this transformation under one atm CO.

Language: Английский

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