Remote C-H Functionalizations by Ruthenium Catalysis
Remote C-H Functionalizations by Ruthenium Catalysis
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DOI：
10.1055/a-1485-5156
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发表时间：
2021-04-19
影响因子：
2.6
通讯作者：
Ackermann, Lutz
中科院分区：
文献类型：
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作者：
Ackermann, Lutz;Samanta, Ramesh C.;Ackermann, Lutz
在过去的几十年中，惰性C-H键的合成转化已经成为分子修饰的有力工具，在制药，材料科学和作物保护方面具有广泛的应用。因此，C-H活化化学的一个关键挑战是完全控制位点选择性。除了通过C-H键的空间位阻或动力学酸度控制底物外，芳烃的位点选择性C-H转化的一个重要方法是通过定向基团使用螯合辅助，从而导致邻近诱导的邻位-C-H金属化。相比之下，更具挑战性的远程C-H激活在Meta位或对位仍然是稀缺的。在这篇综述中，我们展示了钌催化远程C-H激活的独特特征，直到2021年3月，突出了生物相关分子的后期修饰。此外，我们通过实验和计算讨论了重要的机理见解，说明了钌（II）配合物的羧酸盐辅助C-H活化的关键重要性。
Synthetic transformations of otherwise inert C-H bonds have emerged as a powerful tool for molecular modifications during the last decades, with broad applications towards pharmaceuticals, material sciences, and crop protection. Consistently, a key challenge in C-H activation chemistry is the full control of site-selectivity. In addition to substrate control through steric hindrance or kinetic acidity of C-H bonds, one important approach for the site-selective C-H transformation of arenes is the use of chelation-assistance through directing groups, therefore leading to proximity-induced ortho-C-H metalation. In contrast, more challenging remote C-H activations at the meta- or para-positions continue to be scarce. Within this review, we demonstrate the distinct character of ruthenium catalysis for remote C-H activations until March 2021, highlighting among others late-stage modifications of bio-relevant molecules. Moreover, we discuss important mechanistic insights by experiments and computation, illustrating the key importance of carboxylate-assisted C-H activation with ruthenium(II) complexes.