A robust Zintl cluster for the catalytic reduction of pyridines, imines and nitriles.
A robust Zintl cluster for the catalytic reduction of pyridines, imines and nitriles.
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用于催化还原吡啶、亚胺和腈的强大 Zintl 簇。
DOI：
10.1039/d3dt02896h
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发表时间：
2023
期刊：
影响因子：
--
通讯作者：
Van IJzendoorn B
中科院分区：
文献类型：
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作者：
Van IJzendoorn B
尽管p块团簇已经被发现了一个多世纪，但它们作为催化剂介导有机转化的应用尚未得到充分探索。在这里，硼功能化的[P7]簇[(BBN)P7]2−（[1]2−;BBN = 9-硼比环[3.3.1]壬烷）被应用于吡啶的脱芳还原，以及亚胺和腈的硼氢化。这些转化产生胺产物，而胺产物是药品、农用化学品和聚合物的重要前体。催化剂bbb2 -在这些还原中具有很高的稳定性：在喹啉氢硼化中循环使用9次几乎没有导致催化剂性能的损失。催化剂也可以在两种不同的有机转化之间循环使用，同样不会损失催化剂的性能。通过变时间归一化分析和密度泛函理论对吡啶还原机理进行了实验探讨。这项工作表明，Zintl簇可以介导含氮底物的还原在过渡金属无的方式。
Despite p-block clusters being known for over a century, their application as catalysts to mediate organic transformations is underexplored. Here, the boron functionalized [P7] cluster [(BBN)P7]2− ([1]2−; BBN = 9-borabicyclo[3.3.1]nonane) is applied in the dearomatized reduction of pyridines, as well as the hydroboration of imines and nitriles. These transformations afford amine products, which are important precursors to pharmaceuticals, agrochemicals, and polymers. Catalyst [1]2− has high stability in these reductions: recycling nine times in quinoline hydroboration led to virtually no loss in catalyst performance. The catalyst can also be recycled between two different organic transformations, again with no loss in catalyst competency. The mechanism for pyridine reduction was probed experimentally using variable time normalization analysis, and computationally using density functional theory. This work demonstrates that Zintl clusters can mediate the reduction of nitrogen containing substrates in a transition metal-free manner.