Chiral Functionalization of a Zirconium Metal-Organic Framework (DUT-67) as a Heterogeneous Catalyst in Asymmetric Michael Addition Reaction.
Chiral Functionalization of a Zirconium Metal-Organic Framework (DUT-67) as a Heterogeneous Catalyst in Asymmetric Michael Addition Reaction.
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DOI：
10.1021/acs.inorgchem.7b02854
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发表时间：
2018-01
影响因子：
4.6
通讯作者：
K. Nguyen;Christel Kutzscher;Franziska Drache;I. Senkovska;S. Kaskel
中科院分区：
文献类型：
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作者：
K. Nguyen;Christel Kutzscher;Franziska Drache;I. Senkovska;S. Kaskel
DUT-67是一种基于8连接锆和2,5-噻吩二羧酸盐的金属有机骨架（MOF），通过l-脯氨酸的溶剂辅助连接得到了手性碱催化剂。处理5天后，l-脯氨酸几乎完全交换了母体单羧酸盐。结果表明，该手性DUT-67是环己酮与反式β-硝基苯乙烯不对称Michael加成反应的一种很有前景的多相催化剂，产率高达96%，对映选择性与均相反应中的l-脯氨酸相当（ee约为38%）。Zr-MOF可以重复使用至少5次，而结晶度和催化活性没有明显下降。在五个循环中没有检测到催化活性物质进入液相的浸出。
DUT-67, an 8-connected zirconium and 2,5-thiophenedicarboxylate-based metal-organic framework (MOF), was postsynthetically functionalized by l-proline via solvent-assisted linker incorporation to obtain a chiral base catalyst. The parent monocarboxylate could be almost completely exchanged by l-proline after 5 days of treatment. The resulting chiral DUT-67 was demonstrated to be a promising heterogeneous catalyst for the asymmetric Michael addition of cyclohexanone to trans-β-nitrostyrene with excellent yield (up to 96%) and enantioselectivity comparable to that of l-proline in homogeneous reaction (ee of approximately 38%). The Zr-MOF could be reused at least five times without substantial degradation in the crystallinity or catalytic activity. No leaching of catalytically active species into the liquid phase was detected over five cycles.