Highly Mesoporous Metal-Organic Frameworks as Synergistic Multimodal Catalytic Platforms for Divergent Cascade Reactions
Highly Mesoporous Metal-Organic Frameworks as Synergistic Multimodal Catalytic Platforms for Divergent Cascade Reactions
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DOI：
10.1002/anie.201916578
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发表时间：
2020-02-03
影响因子：
16.6
通讯作者：
Lee, In Su
中科院分区：
文献类型：
--
作者：
Dutta, Soumen;Kumari, Nitee;Lee, In Su
对于高效的多步化学反应来说，非常需要在单个纳米结构中合理地设计和吸收不同的化学和生物催化功能，但迄今为止仍然难以捉摸。在这里，我们设计和合成多峰催化纳米反应器（MCNR）的基础上的介孔金属有机框架（MOF）。MCNR由可定制的金属纳米晶体和中孔中稳定锚定的酶以及配位不饱和阳离子金属MOF节点组成，所有这些都在单个纳米反应器空间内。高度紧密和多样化的催化介孔微环境和对MCNR中活性位点的容易接近性使得不同化学和生物催化组分能够合作和协同参与。这通过一锅法多步级联反应显示，该反应涉及非均相催化硝基醛醇反应，随后是[Pd/脂肪酶]催化的化学酶促动态动力学拆分，以定量产率产生光学纯（> 99%ee）硝基醇衍生物。
Rational engineering and assimilation of diverse chemo- and biocatalytic functionalities in a single nanostructure is highly desired for efficient multistep chemical reactions but has so far remained elusive. Here, we design and synthesize multimodal catalytic nanoreactors (MCNRs) based on a mesoporous metal-organic framework (MOF). The MCNRs consist of customizable metal nanocrystals and stably anchored enzymes in the mesopores, as well as coordinatively unsaturated cationic metal MOF nodes, all within a single nanoreactor space. The highly intimate and diverse catalytic mesoporous microenvironments and facile accessibility to the active site in the MCNR enables the cooperative and synergistic participation from different chemo- and biocatalytic components. This was shown by one-pot multistep cascade reactions involving a heterogeneous catalytic nitroaldol reaction followed by a [Pd/lipase]-catalyzed chemoenzymatic dynamic kinetic resolution to yield optically pure (>99 % ee) nitroalcohol derivatives in quantitative yields.