The Biginelli Reaction with an Imidazolium-Tagged Recyclable Iron Catalyst: Kinetics, Mechanism, and Antitumoral Activity
The Biginelli Reaction with an Imidazolium-Tagged Recyclable Iron Catalyst: Kinetics, Mechanism, and Antitumoral Activity
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DOI：
10.1002/chem.201204314
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发表时间：
2013-03-01
影响因子：
4.3
通讯作者：
Neto, Brenno A. D.
中科院分区：
文献类型：
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作者：
Ramos, Luciana M.;Guido, Bruna C.;Neto, Brenno A. D.
本工作介绍了一种新的离子标记的铁催化剂的合成，表征和应用。该催化剂在Biginelli反应中表现出令人印象深刻的性能。当反应在咪唑类离子液体（BMI中心点PF 6、BMI中心点NTf 2和BMI中心点BF 4）中进行时，已经实现了高产率，由此表明离子液体效应在反应中起作用。此外，离子标记的催化剂可以回收和重复使用多达8次，而没有任何明显的活性损失。通过使用高分辨率电喷雾电离四极杆飞行时间质谱（HR-EI-QTOF）和动力学实验进行的机理研究表明，只有一个反应途径，并排除了其他两种可能性的发展条件下。理论计算与铁催化剂的作用机理一致。最后，37种二氢嘧啶酮衍生物，Biginelli反应的产物，在针对MCF-7癌细胞系的测定中评价了它们的细胞毒性，其中一些衍生物的结果令人鼓舞，其对健康细胞系（成纤维细胞）几乎无毒。
The present work describes the synthesis, characterization, and application of a new ion-tagged iron catalyst. The catalyst was employed in the Biginelli reaction with impressive performance. High yields have been achieved when the reaction was carried out in imidazolium-based ionic liquids (BMI center dot PF6, BMI center dot NTf2, and BMI center dot BF4), thus showing that the ionic-liquid effects play a role in the reaction. Moreover, the ion-tagged catalyst could be recovered and reused up to eight times without any noticeable loss in activity. Mechanistic studies performed by using high-resolution electrospray-ionization quadrupole-time-of-flight mass (HR-EI-QTOF) spectrometry and kinetic experiments indicate only one reaction pathway and rule out the other two possibilities under the development conditions. The theoretical calculations are in accordance with the proposed mechanism of action of the iron catalyst. Finally, the 37 dihydropyrimidinone derivatives, products of the Biginelli reaction, had their cytotoxicity evaluated in assays against MCF-7 cancer cell linages with encouraging results of some derivatives, which were virtually non-toxic against healthy cell linages (fibroblasts).