Modulating the Performance of an Asymmetric Organocatalyst by Tuning Its Spatial Environment in a Metal–Organic Framework,Journal of the American Chemical Society

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Modulating the Performance of an Asymmetric Organocatalyst by Tuning Its Spatial Environment in a Metal–Organic Framework
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2017-09-20 , DOI: 10.1021/jacs.7b07921
Lujia Liu ₁ , Tian-You Zhou ₁ , Shane G. Telfer ₁

Affiliation

Systematically tuning the spatial environment around the active sites of synthetic catalysts is a difficult challenge. Here, we show how this can be accomplished in the pores of multicomponent metal-organic frameworks. This relies on embedding a catalytic unit in a pore of the MUF-77 framework and then tuning its environment by introducing different functional groups to the surrounding linkers. This approach benefits from the structural regularity of MUF-77, which places each component in a precise location to circumvent disorder. Prolinyl groups, which are catalytically competent toward asymmetric aldol reactions, were selected as the catalytic unit. Since every prolinyl group is positioned in an identical environment, correlations between the pore architecture and the activity of these single-site catalysts can be elucidated. Systematic engineering of the pore structure, which is achieved by installing modulator groups on the framework linkers, impacts on the reaction rate and the enantiomeric excess of the aldol products. Furthermore, the spatial environment around the proline catalyst can override its innate stereochemical preference to dictate the preferred enantiomer of the reaction product. These results offer a new way to design three-dimensional active site environments for synthetic catalysts.

中文翻译：

通过在金属-有机框架中调节空间环境来调节不对称有机催化剂的性能

系统地调整合成催化剂活性位点周围的空间环境是一项艰巨的挑战。在这里，我们展示了如何在多组分金属有机框架的孔隙中实现这一点。这依赖于将催化单元嵌入 MUF-77 框架的孔中，然后通过将不同的官能团引入周围的连接器来调整其环境。这种方法受益于 MUF-77 的结构规律，它将每个组件放置在一个精确的位置以规避混乱。脯氨酰基对不对称醛醇反应具有催化能力，被选为催化单元。由于每个脯氨酰基团都位于相同的环境中，因此可以阐明孔结构与这些单中心催化剂活性之间的相关性。通过在框架接头上安装调节剂基团实现的孔结构的系统工程影响反应速率和羟醛产物的对映体过量。此外，脯氨酸催化剂周围的空间环境可以超越其先天的立体化学偏好，以决定反应产物的优选对映异构体。这些结果为设计合成催化剂的三维活性位点环境提供了一种新方法。

更新日期：2017-09-20

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