Site-Selective Catalytic Epoxidation of Alkene with Tunable, Atomic Precision by Molecularly Imprinted Artificial Epoxidases.
Site-Selective Catalytic Epoxidation of Alkene with Tunable, Atomic Precision by Molecularly Imprinted Artificial Epoxidases.
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分子印迹人工环氧化酶可调原子精度的烯烃定点催化环氧化反应。
DOI：
10.1021/acscatal.2c00253
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发表时间：
2022-03-18
期刊：
影响因子：
12.9
通讯作者：
Zhao, Yan
中科院分区：
文献类型：
--
作者：
Bose, Ishani;Zhao, Yan
通过其局部化学环境区分化学功能性是酶所掌握的技能，从富含相同类型官能团的肽、核酸和多糖的选择性合成、切割和转化中可以看出。相比之下，合成催化剂通常更擅长基于其电子和空间性质区分官能团。在这里，我们报告人工环氧酶制备通过分子印迹的表面-核心双交联胶束，然后通过高效的功能化的胶束核心中的印迹位点通过光亲和标记。活性位点的大小和形状通过模块化合成的模板进行调整，并准确定位氧输送过氧酸基团。这些催化剂用于烯烃在水中与过氧化氢在温和条件下的环氧化反应，无需任何额外的添加剂。最重要的是，在催化中实现了原子精度，并且使得能够区分碳-碳双键位置相差一个碳的烯烃。
Distinction of chemical functionality by their local chemical environment is a skill mastered by enzymes, evident from the selective synthesis, cleavage, and transformation of peptides, nucleic acids, and polysaccharides that abound with the same type of functional groups. In contrast, synthetic catalysts are generally better at differentiating functional groups based on their electronic and steric properties. Here we report artificial epoxidases prepared through molecular imprinting of surface–core doubly cross-linked micelles, followed by efficient functionalization of the imprinted site in the micellar core via photoaffinity labeling. The size and shape of the active sites are tuned by the modularly synthesized templates, with the oxygen-delivering peroxy acid group positioned accurately. These catalysts are used in epoxidation of alkene in water with hydrogen peroxide under mild conditions, without any additional additives. Most importantly, atomic precision is achieved in the catalysis and enables alkenes to be distinguished that differ in the position of the carbon–carbon double bond by a single carbon.
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