Iridium-Catalyzed Silylation of Aryl C-H Bonds
Iridium-Catalyzed Silylation of Aryl C-H Bonds
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DOI：
10.1021/ja511352u
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发表时间：
2015-01-21
影响因子：
15
通讯作者：
Hartwig, John F.
中科院分区：
文献类型：
--
作者：
Cheng, Chen;Hartwig, John F.
描述了一种铱催化芳基 C-H 键甲硅烷基化的方法。 [Ir(cod)(OMe)](2) 和 2,4,7-三甲基菲咯啉的组合催化 HSiMe(OSiMe3)(2) 与芳烃和杂芳烃的反应，以芳香族化合物作为限制试剂，并具有高水平的空间衍生区域选择性。与之前报道的铑催化的芳基C-H键的硅烷化反应相比，这种新的催化系统对官能团的耐受性要高得多，并且适用于各种杂芳烃。甲硅烷基芳烃产品适合进一步转化，例如氧化、卤化和交叉偶联。复杂药物化合物的后期功能化得到了证实。
A method for the iridium-catalyzed silylation of aryl C-H bonds is described. The reaction of HSiMe(OSiMe3)(2) with arenes and heteroarenes catalyzed by the combination of [Ir(cod)(OMe)](2) and 2,4,7-trimethylphenanthroline occurs with the aromatic compound as the limiting reagent and with high levels of sterically derived regioselectivity. This new catalytic system occurs with a much higher tolerance for functional groups than the previously reported rhodium-catalyzed silylation of aryl C-H bonds and occurs with a wide range of heteroarenes. The silylarene products are suitable for further transformations, such as oxidation, halogenation, and cross-coupling. Late-stage functionalization of complex pharmaceutical compounds was demonstrated.