Kocúrik Martin, Konopáčová Pavlína, Kolman Lukáš, Kryl Pavel, Růžička Aleš, Bartáček Jan, Hanusek Jiří, Váňa Jiří
Institute of Organic Chemistry and Technology, Faculty of Chemical Technology, University of Pardubice, Studentská 573, Pardubice 53210, The Czech Republic.
Department of General and Inorganic Chemistry, Faculty of Chemical Technology, University of Pardubice, Studentská 573, Pardubice 53210, The Czech Republic.
ACS Omega. 2024 Nov 15;9(47):47105-47113. doi: 10.1021/acsomega.4c07485. eCollection 2024 Nov 26.
Aromatic azo compounds stand as a highly sought-after class of substances owing to their extensive array of applications across various fields. Despite their significance, their synthesis often presents challenges, requiring either multistep reactions or being restricted to specific substrate types. In this study, we are showing the universality and mechanistic aspects of a one-step approach for synthesis of nonsymmetrical azoarenes via the Buchwald-Hartwig amination reaction of (pseudo)haloaromatics with arylhydrazines, conducted in the presence of atmospheric oxygen. This reaction protocol yields products in up to 85% yield and is compatible with a wide class of substituents, making it highly adaptable. Notably, the inclusion of BINAP as a ligand plays a pivotal role in achieving favorable outcomes. This study not only offers a versatile solution to a long-standing synthetic challenge but also provides experimental and computational insights into the mechanisms driving the reaction.
芳香族偶氮化合物因其在各个领域的广泛应用而成为一类备受追捧的物质。尽管它们很重要，但其合成往往面临挑战，需要多步反应或仅限于特定的底物类型。在本研究中，我们展示了一种一步法合成非对称偶氮芳烃的通用性和机理方面，该方法是在大气氧存在下，通过（伪）卤代芳烃与芳基肼的布赫瓦尔德-哈特维希胺化反应进行的。该反应方案的产率高达85%，并且与多种取代基兼容，具有高度的适应性。值得注意的是，加入BINAP作为配体在取得良好结果中起着关键作用。这项研究不仅为一个长期存在的合成挑战提供了一种通用的解决方案，还提供了驱动该反应的机理的实验和计算见解。
