Exo-cage catalysis and initiation derived from photo-activating host-guest encapsulation.
Exo-cage catalysis and initiation derived from photo-activating host-guest encapsulation.
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外笼催化和引发源于光激活主客体包封。
DOI：
10.1039/d3sc04877b
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发表时间：
2023-12-13
期刊：
影响因子：
8.4
通讯作者：
Lusby, Paul J.
中科院分区：
文献类型：
--
作者：
Spicer, Rebecca L.;O'Connor, Helen M.;Ben-Tal, Yael;Zhou, Hang;Boaler, Patrick J.;Milne, Fraser C.;Brechin, Euan K.;Lloyd-Jones, Guy. C.;Lusby, Paul J.
配位笼式催化通常依赖于底物的内源结合，利用空腔微环境和空间限制来产生更高的反应活性或感兴趣的选择性。尽管如此，这种方法也存在一些问题，例如经常出现产物抑制或对广泛的底物和反应的适用性有限。在这里，我们描述了一种策略，在该策略中，笼子充当外源催化剂，其中反应物、中间体和产物在整个催化循环过程中保持不受约束。相反，笼子被用来改变辅因子客体的性质，然后将反应性转移到主体相。我们已经用光催化举例说明了这种方法，表明光激活的主客体络合物可以介导[4+2]环加成反应和Aza-Henry反应。详细的原位光解实验表明，笼子既可以作为光引发剂，也可以作为量子产率小于1的循环催化剂。我们报道了一类新的光氧化还原催化剂，它是由非活性配位笼和客体的非共价缔合而产生的。
Coordination cage catalysis has commonly relied on the endogenous binding of substrates, exploiting the cavity microenvironment and spatial constraints to engender increased reactivity or interesting selectivity. Nonetheless, there are issues with this approach, such as the frequent occurrence of product inhibition or the limited applicability to a wide range of substrates and reactions. Here we describe a strategy in which the cage acts as an exogenous catalyst, wherein reactants, intermediates and products remain unbound throughout the course of the catalytic cycle. Instead, the cage is used to alter the properties of a cofactor guest, which then transfers reactivity to the bulk-phase. We have exemplified this approach using photocatalysis, showing that a photoactivated host–guest complex can mediate [4 + 2] cycloadditions and the aza-Henry reaction. Detailed in situ photolysis experiments show that the cage can both act as a photo-initiator and as an on-cycle catalyst where the quantum yield is less than unity. We report a new class of photoredox catalysis arising from the non-covalent association of separately inactive coordination cage and guest.
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影响因子：
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