The hydrogenation of nitroarenes is one of the most important strategies to produce the corresponding anilines and dicyclohexylamines, both of which are the fundamental raw materials in the synthesis of various pharmaceuticals and fine chemicals. Nevertheless, it is still a great challenge to develop a highly versatile and flexible catalytic system to selectively generate desired amines. Herein, we report the solvent-driven selectivity control over a bifunctional Pd/MIL-101 catalyst for the hydrogenation of nitrobenzene. An almost full selectivity of 99.9% to aniline or a surprising selectivity of 99.1% to dicyclohexylamine is achieved by using dimethylformamide (DMF, a polar solvent) or n-hexane (an apolar solvent) as the solvents, respectively. It is proposed that the polarity of solvents can effectively regulate the linkage between reactants/intermediates and Pd/MIL-101, affording controllable selectivities of aniline or dicyclohexylamine at will. In addition, the Lewis acid sites in Pd/MIL-101 can also effectively activate the aromatic ring and accelerate the cross-coupling reaction of amine. This solvent-driven catalytic system also exhibits good recyclability and compatibility for a wide substrate scope in both DMF and n-hexane, showing great promise for industrial applications. This study might open an avenue for the hydrogenation of nitroarenes to selectively produce anilines or dicyclohexylamines by simply regulating the solvent polarity over a bifunctional catalyst system.

中文翻译：

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双功能Pd / MIL-101催化剂上硝基芳烃加氢中苯胺或二环己胺的溶剂驱动选择性控制

硝基芳烃的氢化是生产相应的苯胺和二环己胺的最重要策略之一，它们都是合成各种药物和精细化学品的基本原料。然而，开发高度通用和灵活的催化体系以选择性地产生所需的胺仍然是巨大的挑战。在本文中，我们报告了双官能团Pd / MIL-101催化剂用于硝基苯加氢的溶剂驱动的选择性控制。的99.9％至苯胺或99.1％的令人惊讶的选择性为二环己基胺的几乎完全的选择性是通过使用二甲基甲酰胺（DMF，极性溶剂），或实现ñ-己烷（一种非极性溶剂）分别作为溶剂。提出溶剂的极性可以有效地调节反应物/中间体与Pd / MIL-101之间的键合，任意提供苯胺或二环己胺的可控选择性。此外，Pd / MIL-101中的路易斯酸位点还可以有效激活芳环并促进胺的交叉偶联反应。该溶剂驱动催化体系也表现出良好的再利用性和兼容性在两个DMF广泛的底物范围和Ñ己烷，示出了用于工业应用的巨大潜力。这项研究可能为硝基芳烃的加氢开辟一条途径，以通过在双功能催化剂体系上简单地调节溶剂极性来选择性地生产苯胺或二环己胺。