Nature Communications
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2025
·Vol. 16
·期 1
·1-13
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IF 15.7
Yuan Ziliang,Han Bo,Liu Bing,Sun Jie,Zhou Peng,Mu Rentao,Zhang Zehui
Reductive-coupling of nitro compounds and alcohols is a sustainable route for constructing C = N bonds in organonitrogen chemicals, yet challenging due to the inertness of α-C sp3 -H bond in alcohols and the vulnerability of C = N bonds towards hydrogenation. Here, we report the surprising catalytic activity of ultrafine alkaline-earth metal oxide MgO nanoclusters (0.9 ± 0.3 nm) that efficiently activate α-C sp3 -H bonds, facilitating the transfer hydrogenation and synthesis of value-added chemicals bearing C = N bonds with high to excellent yields (86–99%). Controlled experiments and characterizations showed the crucial role of oxygen vacancies (O v ) and local Mg environment (Mg-O bond) in MgO for substrate adsorption and activation via electronic interactions between substrate’s negatively charged oxygen atoms and O v sites in MgO nanoclusters. Theoretical calculation further confirmed that O v significantly lowered the energy barrier of the hydrogen atom transfer from α-C sp3 -H in ethanol to the nitro group in nitrobenzene (29.3 vs . 52.9 kcal/mol), which is the rate-determining step with the highest energy barrier in reductive-coupling reactions. Our method not only provides an efficient and sustainable pathway for synthesizing organonitrogen chemicals with C = N bonds but also inspires the exploration of main group element catalysts as alternatives to transition metal and noble metal catalysts for organic transformations.
研究领域:
催化化学
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材料科学
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有机合成
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产品关联
DOI
PubMed
高影响因子
Nature Communications
·
2025
·Vol. 16
·期 1
·1-13
·
IF 15.7
He Yingchun,Ma Dong-Dong,Ma Ke,Li Xiaofang,Han Lili,Wu Xin-Tao,Zhu Qi-Long
Electrochemically constructing C–N and N–C–N bonds provides an economical and sustainable alternative to conventional chemosynthesis. Herein, a hierarchically ordered open superstructure of N-doped carbon isolated with accessible three-coordinated Zn single-atom sites is explored for efficient electrocatalytic N–C–N coupling. Benefiting from the distinctive structural merits, this catalyst enables electrocatalytic preparation of N–C–N bonded compounds from methanol and amines. Notably, the Faradaic efficiency and selectivity of N,N,N’,N’ -tetramethyldiaminomethane reach up to 77% and 96% at 0.8 V, respectively. Further integrating the aminoalkylation reaction, an electro-thermo cascade synthesis is explored with the electrochemically obtained N,N,N’,N’ -tetramethyldiaminomethane serving as a unique reagent, leading to a specific set of organonitrogen compounds with (dimethylamino)methyl substituent, including topotecan hydrochloride, an anti-tumor drug, with a high yield of 95%. Furthermore, the in situ spectroscopic characterization and calculations unveil that the under-coordinated Zn-N 3 sites play a pivotal role in stabilizing the key *CH 2 O intermediate, thereby facilitating subsequent nucleophilic addition with amines.
研究领域:
化学
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材料科学
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环境科学
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产品关联
DOI
PubMed
高影响因子
JOURNAL OF MOLECULAR LIQUIDS
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2024
·
IF 5.3
Jiancheng Zhao,Zhaohui Guo,Christian Marcus Pedersen,Lingyu Jia,Shiyu Jia,Xianglin Hou,Yingxiong Wang,Yan Qiao
Organonitrogen chemicals are widely used and in great demand in the food, pharmaceutical and chemical industries. Hence, it is important to develop green and efficient synthesis paths to organonitrogen chemicals for their use as new resources. Herein, we propose the preparation of organonitrogen chemicals from chitin biomass monomer N -acetyl- d -glucosamine (GlcNAc) promoted by natural deep eutectic solvents (NADESs). The selective generation of 3-acetamido-5-(1′,2′-dihydroxyethyl) furan (Chromogen III) and 3-acetamido-5-acetylfuran (3A5AF) from GlcNAc was achieved by the design of NADESs components. GlcNAc reacts in binary NADES proline-glycerol (Pro-Gly) to generate 26 % of Chromogen III and 39 % of 3A5AF in ternary NADES proline-glycerol-lactic acid (Pro-Gly-LA). In addition, the intermolecular hydrogen bonds in NADESs were confirmed through 1 H diffusion-ordered spectroscopy (DOSY) NMR technology. And the results of 13 C NMR chemical shift titration indicated interaction between NADESs and the C3 and C6 position of GlcNAc. Based on the NMR experiments a mechanism is proposed.
研究领域:
生物化学
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绿色化学
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DOI
高影响因子
ANALYTICAL LETTERS
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2023
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IF 2
Zhengyu Wang,Yufeng Hu,Zhiduo Ding,Hao Zhou,Jianye Zhang,Jingjing Zhan,Minghuo Wu
For the identification of trace-level organic nitrogen compounds (NCs) in gasoline, a method consisting of water-assisted dispersive solid-phase extraction (DSPE) and high-performance liquid chromatography-high resolution mass spectrometry was developed in which mixed-mode cation exchange was used as the adsorbent. To increase the DSPE efficiency, water was dispersed into the gasoline to increase the pronation of NCs and enhance the ionic interaction with the adsorbent. After systematic optimization of DSPE conditions, including the adsorbent mass, sample volume, water to gasoline ratio, sample loading time, washing and elution solvents, sensitive determination of NCs (detection limits from 0.1 to 5 ng/L for the 14 analytes) was achieved by this method with a 100-fold enrichment. A number of unknown NC isomers were observed from the extracted ion chromatograms based on the accurate determination of mass-to-charge ratio (m/z), from which two sets of isomers at theoretical m/z of 122.09643 and 136.11208 were selected for identification. By careful elucidation of the product ion spectra of the selected ions, 16 NCs were putatively identified, in which six non-aniline homologs were reported for the first time.
研究领域:
分析化学
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环境科学
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产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）