Mapping boron catalysis onto a phosphorus cluster platform.
Mapping boron catalysis onto a phosphorus cluster platform.
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将硼催化映射到磷簇平台上。
DOI：
10.1039/d2dt03657f
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发表时间：
2022
期刊：
影响因子：
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通讯作者：
Réant BLL
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文献类型：
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作者：
Réant BLL
主族元素，如磷，砷，锗和锡的簇-称为Zintl簇-已经知道了一个多世纪。然而，它们在主族催化中的应用在很大程度上是未知的。在这里，我们将硼烷拴在一个七原子磷簇（{C8 H14} BCH 2CH 2SiMe 2）3 P7（2）上，我们证明了刘易斯酸催化作为硼化学可以使用这种方法映射到簇上的原理证明。催化剂2用于介导关键的有机转化，包括双酰亚胺、异氰酸酯、酮、烯烃、炔和腈的硼氢化。据我们所知，这是Zintl簇作为无金属催化中的无辜平台的第一次应用。通过链接硼，它的化学宝库可以在这些集群中打开。因此，除了催化之外，该方法可以在中子捕获治疗、刺激响应材料和交叉耦合以及受抑刘易斯对和功能聚合物化学中找到主族簇的应用。
Clusters of main group elements, such as phosphorus, arsenic, germanium, and tin – called Zintl clusters – have been known for more than a century. However, their application in main group catalysis is largely unknown. Here, we tether boranes to a seven-atom phosphorus cluster ({C8H14}BCH2CH2SiMe2)3P7 (2) and we demonstrate Lewis acid catalysis as proof-of-principle that boron chemistry can be mapped onto clusters using this method. Catalyst 2 was employed to mediate key organic transformations, including the hydroboration of carbodiimides, isocyanates, ketones, alkenes, alkynes, and nitriles. To the best of our knowledge, this is the first application of Zintl-based clusters as an innocent platform in metal-free catalysis. By chaining boron, its treasure chest of chemistry can be unlocked at these clusters. Hence, beyond catalysis this method could find applications for main group clusters in neutron capture therapy, stimuli responsive materials, and cross-coupling, and frustrated Lewis pair and functional polymer chemistries.