Nickel-Catalyzed Four-Component Carbonylation of 1,3-Butadiene To Access β,γ-Unsaturated Ketones

Organic Letters, Год журнала: 2024, Номер 26(22), С. 4779 - 4783

Опубликована: Май 29, 2024

A new strategy to obtain β,γ-unsaturated ketones via the cross-coupling of 1,3-butadiene, alkyl bromides, and arylboronic acids under 1 bar CO with nickel as catalyst has been developed. This newly developed four-component carbonylation procedure features advantages including using a cheap catalytic system, high step economy, mild reaction conditions, excellent 1,4-regioselectivity, thereby providing sustainable alternative tool for production compared present tactics. To elucidate application potential this method, olefin synthons are derived from representative coupling product.

Язык: Английский

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Single-Electron-Transfer-Mediated Carbonylation Reactions

Accounts of Chemical Research, Год журнала: 2025, Номер unknown

Опубликована: Март 5, 2025

ConspectusTransition-metal-catalyzed carbonylation coupling methods have been accepted as an essential tool for producing carbonylated products over the past few decades. Despite its long-standing history and widespread industrial applications, several challenges remain in chemistry. These include reliance on precious metal catalysts, need of high-energy radiation, difficulties unactivated chemical bonds, etc. As alternative to classic two-electron transfer process, single-electron-transfer (SET)-mediated has emerged a powerful achieve elusive transformations. Over years, commonly available functional handles, such alkenes alkyl halides, via single-electron pathway valuable area research.Our team dedicated developing new reactions using bulk chemicals construct high-value products. broad synthetic motivating us explore SET-mediated transformations two key classes chemicals: alkanes halides. Specifically, our work centered main approaches: (1) Single-electron reduction C(sp3)-X bonds: this strategy leverages activate promoting formation carbon radicals, which turn promotes subsequent addition metals or CO. However, significant challenge lies highly negative potential certain substrates [Ered < -2 V compared saturated calomel electrode (SCE) iodides]. these challenges, intrinsic reducibility CO reactivity various carbonyl-metal intermediates facilitate smooth reaction progress. (2) oxidative C(sp3)-H emphasizes efficiency, high atomic utilization, minimal waste by bypassing traditional preactivation methods. Using 3d we successfully performed aminocarbonylation alkoxycarbonylation wide range bonds (such those aliphatic alkanes, ethers, amines, etc.). The above approaches also enabled radical relay alkenes, allowing precise control pathways. Such improves both efficiency selectivity. advancements transition photoredox catalysis resulting oxyalkylative carbonylation, aminoalkylative fluoroalkylative double rearrangement carbonylation.SET-mediated significantly enhances sustainability scalability process reducing catalysts enabling milder conditions. Additionally, carefully controlling intermediates, fine-tuned produce with This flexibility expands applications chemistry processes. Finally, place particular emphasis application drug discovery, where they serve handles late-stage modification bioactive molecules. applicability enriches toolbox synthesis, efficient functionalization complex versatile approach accelerate discovery novel therapeutic agents, making it critical modern medicinal

Язык: Английский

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Photoredox-catalyzed carbonylative acylation of styrenes with Hantzsch esters

Chemical Communications, Год журнала: 2024, Номер 60(35), С. 4656 - 4658

Опубликована: Янв. 1, 2024

A three-component carbonylation that provides a new method for the synthesis of ketones from Hantzsch esters has been developed.

Язык: Английский

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Visible light-promoted oxycarbonylation of unactivated alkenes

EES Catalysis, Год журнала: 2024, Номер 2(6), С. 1247 - 1252

Опубликована: Янв. 1, 2024

We developed an intermolecular oxygen-centered radical addition carbonylation reaction of unactivated alkenes under visible light irradiation which provides a new strategy to alkenes.

Язык: Английский

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Application of Carbonylation in the Synthesis of Bulk and Fine Chemicals

Chinese Journal of Organic Chemistry, Год журнала: 2024, Номер 44(6), С. 1811 - 1811

Опубликована: Янв. 1, 2024

Язык: Английский

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Palladium-Catalyzed Four-Component Radical Cascade Carbonylation Access to 2,3-Disubstituted Benzofuran Derivatives

Organic Letters, Год журнала: 2024, Номер unknown

Опубликована: Сен. 24, 2024

Multicomponent radical tandem reactions have emerged as a crucial technique for synthesizing complex molecules in organic chemistry. In this study, we report palladium-catalyzed four-component difluoroalkylative carbonylation of enynes and ethyl difluoroiodoacetate. This transformation proceeds through multistep sequential reaction that introduces reactive difluoro carbonyl groups while constructing the benzofuran skeleton. Moreover, variety valuable 2,3-disubstituted derivatives were obtained respectable yields with excellent functional group compatibility.

Язык: Английский

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Trifluoromethylthiolation Carbonylation of Unactivated Alkenes via Distal Migration

Organic Letters, Год журнала: 2024, Номер unknown

Опубликована: Ноя. 20, 2024

Sulfur-containing compounds represent a significant category of organic compounds, and the introduction sulfur groups into can effectively enhance their biological activity synthetic diversity. Although variety difunctionalization reactions alkenes based on radicals have been documented, challenges remain in carbonylative unactivated by addition radical. Herein, we present trifluoromethylthiolative carbonylation reaction alkenes, which goes through trifluoromethylthiol radical to then newly generated carbon intermediate. A heterocyclic/aryl migration presence monoxide is crucial for success this methodology finally resulted formation sulfur-containing carbonylated products good yields.

Язык: Английский

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Four-component regio-divergent carbonylative condensations for the sustainable syntheses of acylhydrazones

Organic Chemistry Frontiers, Год журнала: 2024, Номер 11(14), С. 3833 - 3841

Опубликована: Янв. 1, 2024

Novel catalytic four-component regiodivergent tandem carbonylative condensations of alkenes for the sustainable syntheses acylhydrazones with high atom economy and excellent chemoselectivity have been developed.

Язык: Английский

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Regioselective C-C bond cleavage/aminocarbonylation cascade under copper catalysis

Science China Chemistry, Год журнала: 2024, Номер unknown

Опубликована: Авг. 28, 2024

Язык: Английский

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Low-Valent Tungsten Catalyzed Carbonylative Synthesis of Benzoates from Aryl Iodides and Alcohols

Molecules, Год журнала: 2024, Номер 29(22), С. 5305 - 5305

Опубликована: Ноя. 10, 2024

Non-noble metals catalyzed carbonylative reactions serve as straightforward and sustainable methods for the synthesis of functionalized carbonyl-containing compounds. Herein, a low-valent-tungsten-catalyzed reaction that enables coupling aryl iodides alcohols or phenols was disclosed, employing readily available W(CO)

Язык: Английский

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