Rh-Catalyzed Formal [3 + 2] Cycloaddition Reactions with Cyclopropenones via Sequential C–H/C–C Bond Activation

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

Published: Feb. 13, 2025

The utilization of high-valent metal catalysts to promote cycloaddition reactions involving π bonds through C-C bond activation remains challenging. Despite extensive research, the aldehydes with cyclopropenones catalyzed by complexes has not been documented. Herein, we disclose a novel Rh(III)-catalyzed reaction between and aldehydes, enabling efficient synthesis highly functionalized furanones. A detailed mechanistic investigation was conducted, revealing likely involvement tripodal Rh-carbene intermediate in catalytic cycle, which facilitates product release pathway. This exhibits broad substrate scope, good functional group compatibility, high atom economy, thereby offering versatile general approach construction

Language: Английский

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Synthesis of Indenone-Fused Pyran Derivatives from Aryl Enaminones and Cyclopropenones through Unsymmetrical Relay C–H Bond Activation and Double C–C/C–O Bond Formation

Organic Letters, Journal Year: 2024, Volume and Issue: 26(31), P. 6602 - 6607

Published: July 30, 2024

Presented herein is a novel synthesis of indenone-fused pyran derivatives via the cascade reactions aryl enaminones with cyclopropenones. The formation products involves one-pot procedure consisting C–H bond and enamine functionalization along C–C cleavage cyclopropenone 1,3-rearrangement in situ-formed allylic alcohol moiety followed by intramolecular O-nucleophilic addition Me2NH elimination. To our knowledge, this first simultaneous both indenone scaffolds through concurrent unsymmetrical relay activation double C–C/C–O formation. Moreover, usefulness method further showcased its suitability for large-scale synthetic scenarios diverse transformations products.

Language: Английский

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Pd-Catalyzed Three-Component Coupling of Cyclopropenones via Sequential C–C Bond Activation and Allylation

Organic Letters, Journal Year: 2024, Volume and Issue: 26(20), P. 4262 - 4267

Published: May 9, 2024

A novel Pd-catalyzed three-component domino reaction for the stereoselective synthesis of highly functionalized allyl cinnamates has been developed. In this protocol, a sequential process C–C bond activation and intermolecular allylic substitution was well-organized. The key transformation is in situ generated hydrolysis product cyclopropenone, which triggered new with vinylethylene carbonates. mechanism investigated, demonstrating high stereoselectivity excellent atomic economy process.

Language: Английский

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Pd-catalyzed acylation and allylation of 2-alkynylanilines with 1,2-diphenylcyclopropenones and gem-difluorinated cyclopropanes: a DFT study

Organic Chemistry Frontiers, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

We reported the mechanism of Pd-catalyzed 2-alkynylaniline synthesis into indole by acylation and allylation using density functional theory.

Language: Английский

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Synthesis of Indazole Fused 2-Benzazepines with Polarity-Dependent Fluorescence Based on Formal [4 + 3] Annulation of 3-Aryl-1H-indazoles with Cyclopropenones

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

Published: April 3, 2025

The effective assembly of benzazepine skeletons in a sustainable and atom-economical fashion remains challenging goal modern organic synthesis. Presented herein is novel synthesis indazole fused 2-benzazepine derivatives based on formal [4 + 3] annulation 3-aryl-1H-indazoles with cyclopropenones. formation products proceeds through Ir(III)-catalyzed aryl C-H bond metalation cyclopropenone ring-opening leading to acylation, followed by an intramolecular N-nucleophilic conjugated addition. By using this method, number valuable were effectively generated. This protocol addresses the challenges constructing medium-sized rings cascade C-H/C-C activation C-C/C-N formation. Moreover, photophysical properties thus obtained also evaluated. It turned out that all compounds tested showed solvent polarity-dependent fluorescence features, which could be potentially applied for revealing polarity their immediate environments.

Language: Английский

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Palladium-Catalyzed Regioselective [3 + 2] Annulation with N-Allenamides at the Proximal C═C Bond: Synthesis of γ-Amino-α′-methylenecyclopentenones

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

Published: April 10, 2025

A palladium-catalyzed [3 + 2] cycloaddition of cyclopropenones with N-allenamides has been developed. This methodology facilitates the synthesis γ-amino-α'-methylenecyclopentenones in moderate to excellent yields good regioselectivity and compatibility various functional groups. The employment as versatile 2C synthons enables simultaneous incorporation both a nitrogen atom methylene group into cyclopentenones. Furthermore, this approach exhibits reverse when compared general allenes. Density theory calculations successfully elucidated origin observed regioselectivity.

Language: Английский

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Palladium-catalyzed sequential [3+2] cyclization/C-H activation of o-iodostyrenes with cyclopropenones as C2 synthons

Chemical Communications, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

A novel palladium-catalyzed synthesis of diverse dihydroindeno[2,1- a ]indenes by the sequential [3+2] cyclization/C–H activation o -iodostyrenes with cyclopropenones as C2 synthons is presented.

Language: Английский

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Recent progress in cycloaddition reactions of cyclopropenone

Arabian Journal of Chemistry, Journal Year: 2024, Volume and Issue: 17(8), P. 105845 - 105845

Published: May 23, 2024

Cyclopropenone has emerged as a highly versatile precursor in organic synthesis due to its diverse reactivity. The cyclopropenone derivatives could undergo various transformations such cycloaddition reactions, ring-opening and isomerization reactions the presence of different chemical reagents. Over years, significant progress been made manipulation cyclopropenones for construction carbocycles, heterocycles, other useful compounds. Despite several reviews that have concerned chemistry cyclopropenones, utility motifs carbocycles heterocycles rarely reported. Herein, we report recent advancements synthetic precursors towards compounds with biological significance.

Language: Английский

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Ag-Catalyzed Selective C–C Bond Activation of Cyclopropenones to Access α-Alkylidene Lactones

Organic Letters, Journal Year: 2024, Volume and Issue: 26(29), P. 6120 - 6124

Published: July 11, 2024

A novel Ag-catalyzed ring opening of unsymmetric cyclopropenones for the stereoselective synthesis a diverse range α-alkylidene lactones has been developed. In this protocol, two different C-C(O) bonds were distinguished, demonstrating selective C-C bond activation. This reaction features wide substrate scope, good functional group compatibility, and high atom economy, providing versatile general approach to construction lactones.

Language: Английский

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Solvent-controlled switchable multicomponent tandem oxidative triple functionalization of indolines

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(7), P. 1933 - 1940

Published: Jan. 1, 2024

A new one-pot method for solvent-controlled switchable tandem oxidative triple functionalization of indolines has been developed via successive regioselective chalcogenation, oxidation, amination and halogenation.

Language: Английский

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