The hydroarylation of alkenes with aromatic amines is recognized as the most atom-economical and straightforward approach to obtain functional aromatic amines, which are versatile building blocks in organic synthesis and material chemistry. However, controllable synthesis of single hydroarylation product is still a significant challenge because hydroarylation reaction often delivers four hydroarylation products and hydroamination products are also produced during the reaction. Herein, we report the first example of heterogeneous zeolite catalyzed hydroarylation of styrene and norbornene with aniline derivatives under organic ligand-free conditions. With the USY zeolite as catalyst, a wide scope of alkenes and aromatic amines with various functional groups are smoothly converted into the corresponding products in 48–95% yields with high regioselectivity. Detailed characterizations revealed that Lewis acid can promote Hofmann-Martius rearrangement of hydroamination products toward hydroarylation products, resulting in high selectivity for hydroarylation products. In addition, it could be found that the weak acid sites of zeolite play a key role in forming hydroarylation products. Furthermore, the catalyst can be reused at least 10 times without obvious deactivation. This work may promote the development of heterogeneous catalyst system for alkene hydroarylation.

烯烃与芳族胺的加氢芳基化被认为是获得功能性芳族胺的最经济，最直接的方法，它是有机合成和材料化学中的通用构建基块。但是，单一加氢芳基化产物的可控合成仍然是一个重大挑战，因为加氢芳基化反应通常会产生四种加氢芳基化产物，并且在反应过程中还会产生加氢胺化产物。在此，我们报道了在无有机配体条件下非均相沸石催化苯乙烯和降冰片烯与苯胺衍生物的加氢芳基化的第一个例子。以USY沸石为催化剂，各种具有不同官能团的烯烃和芳族胺可以高区域选择性地以48–95％的收率平稳地转化为相应的产物。详细的表征表明，路易斯酸可以促进加氢胺化产物的Hofmann-Martius重排向加氢芳基化反应，从而提高了对加氢芳基化反应的选择性。另外，可以发现沸石的弱酸位在形成加氢芳基化产物中起关键作用。此外，催化剂可以重复使用至少10次而不会明显失活。这项工作可能会促进烯烃加氢芳基化非均相催化剂体系的发展。对加氢芳基化产物具有高选择性。另外，可以发现沸石的弱酸位在形成加氢芳基化产物中起关键作用。此外，催化剂可以重复使用至少10次而不会明显失活。这项工作可能会促进烯烃加氢芳基化非均相催化剂体系的发展。对加氢芳基化产物具有高选择性。另外，可以发现沸石的弱酸位在形成加氢芳基化产物中起关键作用。此外，催化剂可以重复使用至少10次而不会明显失活。这项工作可能会促进烯烃加氢芳基化非均相催化剂体系的发展。