The selective functionalization of remote C–H bonds in free primary amines holds significant promise for the late-stage diversification of pharmaceuticals. However, to date, the direct functionalization of the meta position of amine substrates lacking additional directing groups remains underexplored. In this Letter, we present a successful meta-C–H arylation of free primary amine derivatives using aryl iodides, resulting in synthetically valuable yields. This meta-selective C–H functionalization is achieved through a sequence involving native amino-directed Pd-catalyzed seven-membered cyclometalation, followed by the utilization of a norbornene-type transient mediator.

中文翻译：

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通过 Pd/降冰片烯催化，天然氨基定向伯胺间位选择性 C–H 芳基化

游离伯胺中远程 C-H 键的选择性官能化为药物的后期多样化带来了巨大的希望。然而，迄今为止，缺乏额外导向基团的胺底物间位的直接官能化仍未得到充分探索。在这封信中，我们展示了使用芳基碘化物对游离伯胺衍生物进行成功的间位-C-H芳基化，从而获得了具有合成价值的产率。这种元选择性 C-H 功能化是通过涉及天然氨基定向 Pd 催化的七元环金属化的序列实现的，然后利用降冰片烯型瞬时介体。