Department of Chemistry, University of Texas at Austin, Austin, TX, 78712, USA.
Angew Chem Int Ed Engl. 2016 Jul 25;55(31):9084-7. doi: 10.1002/anie.201604268. Epub 2016 Jun 8.
Herein, we report the palladium-catalyzed direct arylation of unactivated aliphatic C-H bonds in free primary amines. This method takes advantage of an exo-imine-type directing group (DG) that can be generated and removed in situ. A range of unprotected aliphatic amines are suitable substrates, undergoing site-selective arylation at the γ-position. Methyl as well as cyclic and acyclic methylene groups can be activated. Furthermore, when aniline-derived substrates were used, preliminary success with δ-C-H arylation was achieved. The feasibility of using the DG component in a catalytic fashion was also demonstrated.
在此，我们报告了钯催化的未活化脂肪族 C-H 键在游离伯胺中的直接芳基化反应。该方法利用了一种可以原位生成和去除的外向亚胺型导向基团 (DG)。一系列未保护的脂肪族胺是合适的底物，在 γ-位进行选择性芳基化。甲基以及环和非环亚甲基都可以被活化。此外，当使用苯胺衍生的底物时，δ-C-H 芳基化也取得了初步成功。还证明了 DG 成分在催化方式下的可行性。
