Rajaram Pravien S, Chakkanalil Keerthana, Galloway Jordan, Baxter Ryan D
Department of Chemistry and Biochemistry, University of California, 5200 N. Lake Road, Merced, California 95343, United States.
ACS Org Inorg Au. 2025 May 15;5(4):244-249. doi: 10.1021/acsorginorgau.5c00026. eCollection 2025 Aug 6.
Nitrosoarenes are useful molecules owing to their unique electronic properties. The "NO" functional group is strongly electron-withdrawing, possessing a σ value greater than either the nitro or trimethylammonium functional groups. Although many methods exist for the synthesis of nitroarenes, the direct incorporation of the "NO" functional group in a single step to produce nitrosoarenes has historically received less attention. In this paper, we discuss a mild and selective method for the ipso-nitrosation of arylboronic acids and their derivatives. Depending on the substrate identity, both nitro and nitrosoarenes can be formed from arylboronic acids. To overcome substrate-controlled selectivity, we developed a one-pot, two-step procedure to exclusively produce nitrosoarenes from boronic acids with no evidence of unwanted nitroarene products. A variety of arenes and heteroarenes are selectively nitrosated in good yields via reactions run open to air and without protection from moisture.
亚硝基芳烃因其独特的电子性质而成为有用的分子。“NO”官能团具有很强的吸电子性，其σ值大于硝基或三甲基铵官能团。虽然存在许多合成硝基芳烃的方法，但在一步反应中直接引入“NO”官能团来制备亚硝基芳烃在历史上受到的关注较少。在本文中，我们讨论了一种温和且选择性的方法，用于芳基硼酸及其衍生物的原位亚硝化反应。根据底物的特性，芳基硼酸既可以生成硝基芳烃，也可以生成亚硝基芳烃。为了克服底物控制的选择性问题，我们开发了一种一锅两步法，能够从硼酸中专门制备亚硝基芳烃，且没有 unwanted 硝基芳烃产物生成的迹象。通过在空气中敞口进行且无需防潮保护的反应，多种芳烃和杂芳烃能够以良好的产率被选择性亚硝化。
