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l-proline modulated zirconium metal organic frameworks: Simple chiral catalysts for the aldol addition reaction
Journal of Catalysis ( IF 6.5 ) Pub Date : 2018-06-28 , DOI: 10.1016/j.jcat.2018.06.013
Xiao Feng , Himanshu Sekhar Jena , Karen Leus , Guangbo Wang , Judith Ouwehand , Pascal Van Der Voort

Three l-proline modulated zirconium based MOFs denoted as UiO-66, Zr-NDC (NDC = 2,6-Naphthalenedicarboxylate) and UiO-67 were synthesized, characterized and explored as heterogeneous catalyst in diastereoselective aldol addition reactions between 4-nitrobenzaldehyde and linear/cyclic ketones. Upon l-proline modulation, chirality was introduced into these Zr-MOFs which were consequently explored as chiral catalysts for asymmetric reactions. A systematic study was conducted to look into the effect of the synthesis temperature on the modulation in each Zr-MOF. The modulated UiO-66 material synthesized at 120 °C exhibited full conversion and a good diastereoselectivity whereas the homogeneous l-proline catalyst showed only 61% conversion and a reversed diastereoselectivity. The catalyst exhibited no leaching of the catalytically active species and was reused for at least three additional cycles. The observed high catalytic activity is a result of the electron withdrawing nature of the Zr-node coordinated to l-proline.



中文翻译:

l-脯氨酸调节的锆金属有机骨架:用于醛醇加成反应的简单手性催化剂

-脯氨酸调制锆表示为UIO-66,Zr的NDC(NDC = 2,6-萘二甲酸)和UIO-67合成,表征和探索作为4-硝基苯甲醛和线性之间在非对映选择性醛醇加成反应的非均相催化剂基于的MOF /环酮。在1-脯氨酸调节后,将手性引入这些Zr-MOF中,因此将其用作不对称反应的手性催化剂。进行了系统的研究,以研究合成温度对每个Zr-MOF中调制的影响。在120℃下合成的调制UIO-66材料显示完全转化和良好的非对映选择性而均匀的-脯氨酸催化剂仅显示61%的转化率和反向的非对映选择性。该催化剂没有显示出催化活性物质的浸出,并且至少重复使用了三个额外的循环。观察到的高催化活性是与1-脯氨酸配位的Zr-节点的电子吸收性质的结果。

更新日期:2018-06-28
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