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JOURNAL OF ORGANIC CHEMISTRY · 2021 · IF 4.354

Iron-Catalyzed Oxidative Amination of Benzylic C(sp3)–H Bonds with Anilines

Yan-Ling Song,Bei Li,Zhen-Biao Xie,Dan Wang,Hong-Mei Sun

Iron-catalyzed oxidative amination of benzylic C(sp3)–H bonds with anilines bearing electron-withdrawing groups (EWGs) or electron-donating groups (EDGs) is realized based on simple variations of N-substituents on imidazolium cations in novel ionic Fe(III) complexes. The structural modification of the imidazolium cation resulted in regulation of the redox potential and the catalytic performance of the iron metal center. Using DTBP as oxidant, [HItBu][FeBr4] showed the highest catalytic activity for anilines bearing EWGs, while [HIPym][FeBr4] was more efficient for EDG-substituted anilines. This work provides alternative access to benzylamines with the advantages of both a wide substrate scope and iron catalysis.

CAS / MDL: 62-53-3
研究领域: 有机化学 · 催化化学
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Catalysis Science & Technology · 2025 · IF 4.2

Efficient upgrading of polystyrene plastics to nitriles through a catalytic oxidative amination process

Chengyang Sun,Yong Guo,Xiaohui Liu,Yanqin Wang

The upcycling of C–C bond linked polyolefins has drawn wide attention in recent years and a lot of studies have been focused on the conversion of polyolefins to hydrocarbons, while the further valorization to more value-added products has barely been developed. In this work, we developed an efficient strategy to upgrade polystyrene (PS) plastics into a single N-containing product, benzonitrile, over a NiO/CeO2 catalyst via a one-pot, two-step process. The first step is the oxidative-amination of PS to a mixture of benzamide and benzonitrile and the second step is the dehydration of benzamide to benzonitrile; finally, a single N-containing product, benzonitrile with a 50.3% yield, was achieved. Mechanism studies via control experiments in the first oxidative-amination step showed that benzaldehyde was the important intermediate, which can undergo two parallel pathways generating benzamide and benzonitrile, respectively. Following the dehydration of benzamide to benzonitrile in the second step, benzonitrile was produced as the only product. This strategy can also be extended to real-life PS plastics and a high yield of benzonitrile was achieved. This novel study provides an efficient approach for upgrading waste plastics to a single high-value product.

CAS / MDL: 1306-38-3
研究领域: 化学工程 · 环境科学 · 催化科学
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CHEMICAL ENGINEERING SCIENCE · 2022 · IF 4.889

Green, versatile, and scale-up synthesis of amides by aerobic oxidative amination over Ag2O/P-C3N4 photocatalyst

Lanqing Deng,Lang Chen,Liangdi Zhu,Yang Li,Jie Ou-Yang,Shaofeng Wu,Peng Chen,Sheng Shen,Junkang Guo,Yongbo Zhou,Chak-Tong Au,Shuang-Feng Yin

Being extensively applied in various fields of chemistry and chemical industry, the development of a green and versatile method for the synthesis of amides is in line with the demand of sustainable chemistry. Herein, a direct, highly selective, and scale-up (5–20 mmol) method for photocatalytic synthesis of amides through aerobic oxidative amination of alcohols with amines was developed under visible light, room temperature, using air as the oxidant. Benefiting from the adsorption of sodium hemiaminal on catalyst lengthens the C H bond (1.148 Å), this novel process is feasible for a broad range of functionlized amides (69 examples), especially those for drug manufacture (e.g., moclobemide and pipobroman). Imines was almost prevented with excellent amide selectivity up to 99 % could be ascribed to the low energy barrier for hemiaminal dehydrogenation while that for dehydration is high (2.13 eV). This green and efficient protocol represents an ideal alternative to the currently known methods.

CAS / MDL: 14898-67-0 15529-49-4
研究领域: 有机化学 · 催化化学 · 环境化学
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Current Protocols · 2021 ·Vol. 1 ·期 10 ·e274 · IF 0

Post-Synthetic Modification of Oligonucleotides Through Oxidative Amination of 4-Thio-2′-Deoxyuridine

Jingyi Wang,Jiachen Shang,Yu Xiang,Aijun Tong

Functionalized oligonucleotides (ONs) are widely applied as target recognition molecules for biosensing and gene regulation. Herein, we describe a general method for post-synthetic modification of ONs based on the oxidative amination of 4-thio-2′-deoxyuridine (4SdU) with sodium periodate and several amines. Alkyne-/azide-, biotin-, and fluorophore-modified ONs were prepared by modifying 4SdU-containing ONs with the corresponding amines and characterized for their bioorthogonal reactivity, streptavidin-binding affinity, and fluorescence properties, respectively. We synthesized three fluorophore-modified ONs with and without the aromatic fluorophores conjugated to modified nucleobases and investigated their emission properties. © 2021 Wiley Periodicals LLC. Basic Protocol 1 : Post-synthetic modification of ONs Supporting Protocol : Preparation of dansyl ethylenediamine Basic Protocol 2 : Quantification of ON reaction yields Basic Protocol 3 : Characterization of modified ONs

研究领域: 生物化学 · 分子生物学 · 化学生物学
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CHINESE JOURNAL OF CHEMISTRY · 2017 ·Vol. 35 ·期 6 ·984-990 · IF 1.852

Catalytic Amidation of 5-Hydroxymethylfurfural to 2,5-Furandicarboxamide over Alkali Manganese Oxides

Xiaofang Li,Xiuquan Jia,Jiping Ma,Yongming Xu,Yizheng Huang,Jie Xu

2,5-Furandicarboxamide was firstly synthesized in yield of 85% via catalytic oxidative amidation of 5-hydroxymethylfurfural with aqueous NH 3 over alkali manganese oxides of α -MnO 2 /Na x MnO 2 . The intermediates of 5-hydroxymethyl-furonitrile, 2,5-dicyanofuran, and 5-cyano-2-furancarboxamide were verified and their reactivities were further examined. The kinetic analysis results showed that the transformation of intermediate product of 5-cyano-2-furancarboxamide to 2,5-furan-dicarboxamide is a slower step, which is closely relative to the reaction temperature and basicity of catalyst.

CAS / MDL: 1317-35-7 1317-34-6
研究领域: 化学工程 · 催化化学
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ACS Catalysis · 2021 · IF 13.084

Direct Oxidative Amination of the Methyl C–H Bond in N-Heterocycles over Metal-Free Mesoporous Carbon

Xiangdong Long,Jia Wang,Guang Gao,Chao Nie,Peng Sun,Yongjie Xi,Fuwei Li

Direct oxidative amination of the sp3 C–H bond is an attractive synthesis route to obtain amides. Conventional catalytic systems for this transformation are based on transition metals and complicated synthesis processes. Herein, direct and efficient oxidative amination of the methyl C–H bond in a wide range of N-heterocycles to access the corresponding amides over metal-free porous carbon is successfully developed. To understand the fundamental structure–activity relationships of carbon catalysts, the surface functional groups and the graphitization degree of porous carbon have been purposefully tailored through doping with nitrogen or phosphorus. The results of characterization, kinetic studies, liquid-phase adsorption experiments, and theoretical calculations indicate that the high activity of the carbon catalyst is attributed to the synergistic effect of surface acidic functional groups (hydroxyl/carboxylic acid/phosphate) and more graphene edge structures exposed on the surface of carbon materials with a high graphitization degree, in which the role of acidic functional groups is to adsorb the substrate molecule and the role of the graphene edge structure is to activate O2.

CAS / MDL: 83-86-3
研究领域: 有机化学 · 催化化学
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JOURNAL OF MOLECULAR LIQUIDS · 2025 · IF 5.2

Reversible pH-responsive Pickering emulsions stabilized by amine oxide-functionalized nanoparticles: interfacial regulation and stabilization mechanisms

Haihua Pei,Yuhui Wu,Jianwei Zhao,Jian Zhang,Yang Liu,Zhanlei Ma,Guicai Zhang

This study introduces a novel pH-responsive Pickering emulsion system stabilized by lauramidopropyl amine oxide (LAO)-functionalized SiO₂ nanoparticles, demonstrating reversible stabilization controlled by LAO's protonation state. At pH 7, the protonated cationic LAO electrostatically adsorbs onto nano-SiO₂ surfaces, imparting optimal amphiphilicity (θ = 87.6°). The resulting interfacial stabilization is attributable to three synergistic mechanisms: (1) enhanced electrostatic nanoparticle adhesion, (2) hydrophobic shielding by oriented lauryl chains, and (3) mechanical reinforcement via nanoparticle aggregation at the interface. When the pH is increased to 10, LAO deprotonation induces complete demulsification due to interfacial film disintegration. Zeta potential measurements, interfacial rheology, and confocal laser scanning microscopy (CLSM) have been employed to confirm the system's fully reversible pH response (7 ↔ 10) over multiple cycles, with >80 % efficiency retention even at ultralow LAO concentrations (0.1 mM). The system's exceptional recyclability and rapid pH response, in conjunction with minimal surfactant requirements, establish it as a sustainable platform for applications such as enhanced oil recovery. Furthermore, it serves as a fundamental framework for designing smart, stimulus-responsive materials with tunable stability and reversible properties.

CAS / MDL: 1330-20-7
研究领域: 胶体与界面科学 · 材料科学 · 化学工程 · 软物质物理 · 纳米技术
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ACS Catalysis · 2025 · IF 13.1

Redox Heterocluster-Based Frameworks for One-Pot Photocatalytic C(sp3)-H Bond Oxidative Imination

Yu-Yang Liu,Shan Xu,Xiao-Xin Li,Run-Han Li,Xin-Ting Cai,Hui-Zhen Zhong,Jiang Liu,Qing Huang,Lei Zhang,Shun-Li Li,Ya-Qian Lan

Developing strategies and photocatalysts for C(sp3)-H bond functionalization under simple and mild conditions is important but challenging. Here, we report two redox heterocluster-based frameworks, named Ni5-PW12 and Ni5-V16, in which the terminal oxygen atoms of polyoxometalates are directly coordinated to metal atoms in metal–organic clusters. Due to the coexisting strong oxidation and reduction capacities, both of these photocatalysts achieve photocatalytic C(sp3)-H bond oxidative imination through combining oxidation of methyl aromatics and reduction of nitro aromatics reactions. The experimental and theoretical results reveal that benefiting from the short distance between the clusters, the rapid charge transfer and mass transfer processes would enhance the photocatalytic reactivity and inhibit side reactions. More importantly, all of the photocatalytic reactions are carried out in mild conditions at room temperature without any additional solvents, photosensitizers, oxidizing or reducing agents, or cocatalysts.

CAS / MDL: 10034-93-2
研究领域: 光催化 · 有机合成 · 材料化学 · 簇化学
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