A bifunctional molecular catalyst built up of l-proline grafted polyoxometalate for one-pot three-component green synthesis of heterocycles
A bifunctional molecular catalyst built up of l-proline grafted polyoxometalate for one-pot three-component green synthesis of heterocycles
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DOI：
10.1039/d3gc00951c
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发表时间：
2023-06-07
期刊：
影响因子：
9.8
通讯作者：
Wei, Yongge
中科院分区：
文献类型：
--
作者：
Dai, Guoyong;Li, Qi;Wei, Yongge
多金属氧酸盐（POMs）和有机小分子催化剂在化学合成中都表现出优异的性能。纳米级聚甲醛和有机催化剂的结合可以充分发挥它们各自的优点，并使难以捉摸的反应在一个催化系统中实现。然而，这两种组分的共价组合很少被探索。本文首次将l-脯氨酸接枝到Mn-Anderson POM上，成功设计并合成了一种双功能纳米分子催化剂l-Pro-Mn-Anderson，催化实验表明，l-Pro-Mn-Anderson可以实现一锅醇氧化/三组分反应，合成两类杂环化合物（5-芳基嘧啶[4,5-b]喹啉二酮衍生物和吡唑啉[3,4-b]吡啶衍生物），产率高达97%。催化剂的详细表征和催化机理表明，l-Pro-Mn-Anderson表现出有机和无机催化功能相结合的协同效应，共价键提高了分子催化剂的整体氧化还原活性。本研究为设计和应用共价组合有机-无机分子催化剂进行从头有机合成开辟了一条新途径。
Both polyoxometalates (POMs) and organic small molecular catalysts show excellent performance in chemical synthesis. The incorporation of nanoscale POMs and organocatalysts allows the full expression of their respective merits and enables elusive reactions to be achieved in one catalytic system. However, the covalent combination of such two components has been rarely explored. Here, we have successfully designed and synthesized a bifunctional nanomolecular catalyst l-Pro-Mn-Anderson by grafting l-proline onto an Mn-Anderson POM for the first time, and catalytic experiments show that l-Pro-Mn-Anderson can realize the one-pot alcohol oxidation/three-component reaction to synthesize two types of heterocyclic compounds (5-aryl-pyrimido[4,5-b]quinoline-dione derivatives and pyrazolo[3,4-b] pyridine derivatives) in high yields up to 97%. The detailed characterization of the catalyst and the catalytic mechanism has shown that l-Pro-Mn-Anderson exhibits synergistic effects that combine both organic and inorganic catalytic functions, and the covalent linkage improves the overall redox activity of the molecular catalyst. This study opens up a new way for the design and application of covalently combined organic-inorganic molecular catalysts toward de novo organic synthesis.