Heterocyclic Suzuki–Miyaura coupling reaction of metalla-aromatics and mechanistic analysis of site selectivity

Zhang, Hong; Lin, Zuzhang; Cai, Yapeng; Zhang, Yaowei; Xia, Haiping

doi:10.1039/d2sc05455h

Cited by 4 publications

(1 citation statement)

References 77 publications

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“…Generally, carbon-carbon bond in organic compounds is done through Suzuki coupling reduction reactions using palladium as catalyst [1][2][3]. Pyrazole skeleton functions as the backbone in various felds such as natural products, functional materials agrochemicals, and pharmaceuticals [4].…”

Section: Introductionmentioning

confidence: 99%

Nano-Pd/Chitosan Composite: An Extremely Effective Catalyst to the Synthesis of Pyrazolyl Analogues through Suzuki–Miyaura Cross-Coupling Reactions in an Aqueous Medium

Senthilkumar

Manisankar

Pandimurugan³

et al. 2023

Journal of Chemistry

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Substituted pyrazolyl derivatives were synthesized through Suzuki cross coupling of aromatic boronic acid with heterocyclic halide using newly synthesized nano-Pd/chitosan catalyst by the water-mediated green synthesis methodology. The reactivity of the nano-Pd catalyst was highly enhanced by incorporating palladium nanoparticles with a biopolymer chitosan matrix. The synthesized nano-Pd/chitosan catalyst was studied thoroughly for its structure, morphology, and other fundamental aspects such as the size and shape by various techniques including XRD, FESEM, and EDAX analyses. The scope of the catalyst was disclosed by their great stability with remarkable reusability for Suzuki cross-coupling reaction with twelve different boronic acids under the green synthetic methodology.

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Section: Introductionmentioning

confidence: 99%

Nano-Pd/Chitosan Composite: An Extremely Effective Catalyst to the Synthesis of Pyrazolyl Analogues through Suzuki–Miyaura Cross-Coupling Reactions in an Aqueous Medium

Senthilkumar

Manisankar

Pandimurugan³

et al. 2023

Journal of Chemistry

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Carbonylation Reactions of a Metallapentalyne: Synthesis of Its Ester and Amide Derivatives

Zhu,

Chen,

Luo

et al. 2024

Chin. J. Chem.

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Comprehensive SummaryCarbonylation reactions are a valuable synthetic method to construct carbonyl compounds and carbonylation reactions of aryl halides stand out as a highly significant tool for generating carbonyl substituted arenes. However, the important reactions have never been realized in aromatic metallacycles. Herein, we present the first carbonylation reactions of metallaaromatics, specifically alkoxycarbonylation and aminocarbonylation reactions of an osmapentalyne. During the carbonylation process, the electronic and steric properties of nucleophiles are regarded as critical factors. The alcohols with bulky substituents (isopropanol) require more reaction time and tert‐butyl alcohol is inert in the reaction. Comparatively, amines, being stronger nucleophiles, exhibit divergent behaviors. Bulky amines undergo aminocarbonylation, whereas small amines prefer direct nucleophilic additions. Control experiments revealed that the intermediate derived from coupling of metal carbyne with CO plays a significant role in the carbonylation reaction. According to these observations, a divergent pathway for the reaction is proposed. Furthermore, the photophysical properties of these carbonyl‐functionalized osmapentalene complexes are studied, and the maximum absorption peak of compound with a carboxylic group exhibits a significant red‐shift due to the smaller HOMO‐LUMO gap. These findings contribute to expanding the reactivity of metallaaromatics and offer new opportunities for the synthesis of carbonyl‐functionalized metallacycles.

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Synthesis of Methylated, Hydroxylated, and Aminated Metallaaromatics via Ring-Opening Reactions of the Fused Three-Membered Ring Units

Fei,

Ma,

Ruan

et al. 2024

Organometallics

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The development of efficient functionalization methods for metallaaromatics is pivotal in manipulating their structural and chemical properties. While introducing hydroxyl and amino moieties into metallaaromatics is highly desirable, relevant reports remain scarce. In our approach, we exploit the reaction of hydroxylamine with a fused compound composed of a metallapentalene moiety and an unsaturated three-membered metallacycle. Upon exposure to air, hydroxylamine is oxidized by heating and forms a nitrosyl anion that replaces the chloride ligand within this system. The ligand exchange triggers the ring opening of the three-membered metallacycles, which is then followed by protonation, thereby generating a series of methylated, hydroxylated, and aminated metallaaromatic derivatives. This sequential process is accompanied by dearomatization and rearomatization within the metallapentalene frameworks, demonstrating the versatility of this new functionalization methodology.

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Heterocyclic Suzuki–Miyaura coupling reaction of metalla-aromatics and mechanistic analysis of site selectivity

Abstract: Pd-catalyzed Suzuki-Miyaura cross-coupling is one of the most straightforward and versatile methods for the construction of functionalized arenes and heteroarenes but site-selective cross-coupling of polyhalogenated (hetero)arenes containing identical halogen substituents...

Cited by 4 publications

References 77 publications

Nano-Pd/Chitosan Composite: An Extremely Effective Catalyst to the Synthesis of Pyrazolyl Analogues through Suzuki–Miyaura Cross-Coupling Reactions in an Aqueous Medium

Nano-Pd/Chitosan Composite: An Extremely Effective Catalyst to the Synthesis of Pyrazolyl Analogues through Suzuki–Miyaura Cross-Coupling Reactions in an Aqueous Medium

Carbonylation Reactions of a Metallapentalyne: Synthesis of Its Ester and Amide Derivatives

Synthesis of Methylated, Hydroxylated, and Aminated Metallaaromatics via Ring-Opening Reactions of the Fused Three-Membered Ring Units

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