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用于二氢吡啶和二氢喹唑啉酮有氧脱氢的单铁原子与DDQ催化剂体系。

The single Fe atoms and DDQ catalyst system for the aerobic dehydrogenation of dihydropyridines and dihydroquinazolinones.

作者信息

Veisi Hamzeh, Rostami Amin

机构信息

Department of Chemistry, Faculty of Science, University of Kurdistan, Sanandaj, Iran.

Research Center for Nanotechnology, University of Kurdistan, Sanandaj, Iran.

出版信息

Sci Rep. 2025 Jul 2;15(1):22673. doi: 10.1038/s41598-025-03750-w.

Abstract

Single-atom nanozymes (SAzymes) made of iron show great potential as artificial enzymes due to their consistent active sites closely resembling the active centers found in natural enzymes. They can be produced from accessible and affordable raw materials, making them suitable options for various applications. In the present research, Iron single-atom anchored N-doped carbon (Fe-N-C) as a laccase-mimicking nanozyme was prepared using 2-methylimidazole, Zinc nitrate, and Iron(II) chloride and characterized using various techniques. Fe-N-C/DDQ was used as a bioinspired oxidative cooperative catalytic system for the oxidation of 1,4-dihydropyridine and 2,3-dihydroquinazolinones to pyridines (87-96% yield), and quinazolinones (82-94% yield), respectively, with O as a suitable oxidant in water/acetonitrile at room temperature. The main advantages and novelties of this method are: (1) this is the first time that the Fe-N-C SAzyme/DDQ catalyst system has been used for the aerobic oxidation of N-heterocyclic compounds (2) oxidation of a wide range of 1,4-dihydropyridines and 2,3-dihydroquinazolinones were performedusing an ideal oxidant with good to high yields under mild conditions (3) Fe-N-C SAzyme was prepared using a simple method and available and inexpensive raw materials system (4) Fe-N-C SAzyme couples the benefits of heterogeneous (easy separation and reusability) and homogeneous catalysts (high activity and reproducibility).

摘要

由铁制成的单原子纳米酶(SAzymes)作为人工酶具有巨大潜力,因为其一致的活性位点与天然酶中的活性中心极为相似。它们可以由易得且经济的原材料制备,使其成为各种应用的合适选择。在本研究中,使用2-甲基咪唑、硝酸锌和氯化亚铁制备了作为模拟漆酶纳米酶的铁单原子锚定氮掺杂碳(Fe-N-C),并采用各种技术对其进行了表征。Fe-N-C/DDQ被用作一种受生物启发的氧化协同催化体系,在室温下于水/乙腈中,以氧气作为合适的氧化剂,将1,4-二氢吡啶和2,3-二氢喹唑啉酮分别氧化为吡啶(产率87-96%)和喹唑啉酮(产率82-94%)。该方法的主要优点和新颖之处在于:(1)这是首次将Fe-N-C SAzyme/DDQ催化剂体系用于氮杂环化合物的需氧氧化;(2)在温和条件下,使用理想的氧化剂对多种1,4-二氢吡啶和2,3-二氢喹唑啉酮进行氧化,产率良好至高;(3)Fe-N-C SAzyme采用简单方法制备,使用的是可得且廉价的原材料体系;(4)Fe-N-C SAzyme兼具多相催化剂(易于分离和可重复使用)和均相催化剂(高活性和可重复性)的优点。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d6c8/12216217/f0005906b88c/41598_2025_3750_Sch1_HTML.jpg

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