Polyoxometalate-based homochiral metal-organic frameworks for tandem asymmetric transformation of cyclic carbonates from olefins.
Polyoxometalate-based homochiral metal-organic frameworks for tandem asymmetric transformation of cyclic carbonates from olefins.
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基于多金属氧酸盐的纯手性金属有机骨架用于从烯烃串联不对称转化环状碳酸酯
DOI：
10.1038/ncomms10007
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发表时间：
2015-12-18
影响因子：
16.6
通讯作者：
Duan C
中科院分区：
文献类型：
--
作者：
Han Q;Qi B;Ren W;He C;Niu J;Duan C
目前，人们对开发自动串联催化反应非常感兴趣，即在不改变任何反应条件的情况下，通过不同的机械反应来催化转移底物。通过将吡咯烷部分作为手性有机催化剂和多金属氧酸盐作为氧化催化剂，设计了一种有效的串联催化剂，用于将二氧化碳有效地转化为具有增值作用的对映体纯环状碳酸酯。多个催化中心在骨架中有序分布且空间匹配。捕获的CO2分子被位置良好的吡咯烷和胺基团协同固定和激活，提供了与末端W=O活化的环氧化中间体的进一步相容，并以单一的准备阶段和不对称的方式驱动串联催化过程。该方法结构简单，使用廉价易得的化学试剂，为开发实用的同手性二氧化碳转化材料提供了极大的希望。
Currently, great interest is focused on developing auto-tandem catalytic reactions; a substrate is catalytically transferred through mechanistically distinct reactions without altering any reaction conditions. Here by incorporating a pyrrolidine moiety as a chiral organocatalyst and a polyoxometalate as an oxidation catalyst, a powerful approach is devised to achieve a tandem catalyst for the efficient conversion of CO2into value-added enantiomerically pure cyclic carbonates. The multi-catalytic sites are orderly distributed and spatially matched in the framework. The captured CO2molecules are synergistically fixed and activated by well-positioned pyrrolidine and amine groups, providing further compatibility with the terminal W=O activated epoxidation intermediate and driving the tandem catalytic process in a single workup stage and an asymmetric fashion. The structural simplicity of the building blocks and the use of inexpensive and readily available chemical reagents render this approach highly promising for the development of practical homochiral materials for CO2conversion.