Cobalt-Catalyzed Enantioselective Desymmetrization and Chemodivergent Parallel Kinetic Resolution of Unsaturated Substrates via C(sp³)–H Bond Activation

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 3860 - 3872

Published: Feb. 19, 2025

Language: Английский

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Harnessing Halide Ligands and External Electric Fields in Cobalt-Catalyzed Oxidative Cyclometalation: Mechanistic Insights and Reactivity Modulation

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

Published: March 12, 2025

This study explores the roles of halide ligands and external electric fields (EEFs) in tuning reactivity cobalt-catalyzed oxidative cyclometalation (OCM) 1,6-enynes, focusing on concerted mechanism. Using density functional theory (DFT), we investigate how these factors influence key processes OCM step, particularly cleavage π bonds, formation M-C creation a new C-C bond. Our findings show that polar solvents lower activation barriers, while increase them, inhibiting reaction by weakening back-donation reducing orbital overlap. However, strategic application EEFs counteracts this inhibition, enhancing electron back-donation, stabilizing transition state, facilitating bond formation. The Dewar-Chatt-Duncanson (DCD) model, distortion/interaction analysis, quantum atoms molecules (QTAIM) delocalization index (DI) calculation reveal reduce cobalt center, π-back-donation raising energy barriers. work provides insights into electronic geometric can be manipulated to optimize catalytic performance synthetic transformations.

Language: Английский

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Photoredox cobalt-catalyzed asymmetric desymmetric reductive coupling of cyclobutenes with alkynes

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: April 1, 2025

Catalytic methods to couple alkynes and alkenes are highly valuable in synthetic chemistry. The cobalt-catalyzed intermolecular reductive coupling of is particularly attractive due the unique reactivity cost-effectiveness cobalt catalysts. However, enantioselective transformations this kind less developed. limited successful examples restricted use electronically biased activated olefins as partners. Herein, we report an asymmetric desymmetric unbiased succinimide-containing cyclobutenes with synthesize enantioenriched, synthetically important vinyl cyclobutanes via photoredox dual catalysis. Excellent enantioselectivities, good diastereoselectivities regioselectivities obtained. Preliminary mechanistic studies suggest that Hantzsch ester a better reducing reagent when used combination Et3N. Density functional theory calculations reveal reaction proceeds more likely through Co(III)-H migratory insertion mechanism. Here, authors internal

Language: Английский

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Hydroarylative cyclization of enynes with aromatic ketones catalyzed by a low-valent iron-phosphine complex

Tetrahedron Letters, Journal Year: 2024, Volume and Issue: unknown, P. 155409 - 155409

Published: Dec. 1, 2024

Language: Английский

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