Liu Qianrui, Jiang Jiaming, Ye Xuanzeng, Sun Jiawen, Wu Yao, Shao Yinlin, Deng Chao, Zhang Fangjun
School of Pharmaceutical Sciences, Wenzhou Medical University, Wenzhou 325035, China.
College of Chemistry and Materials Engineering, Wenzhou University, Wenzhou 325035, China.
J Org Chem. 2023 Aug 4;88(15):10632-10646. doi: 10.1021/acs.joc.3c00669. Epub 2023 Jul 14.
Simple, commercially available iodine was successfully employed as a highly efficient and chemoselective catalyst for the oxidative annulation of β,γ-unsaturated hydrazones to produce 1,6-dihydropyridazines under mild conditions for the first time. Interestingly, when active β,γ-unsaturated hydrazone compounds containing electron-donating groups, such as furyl, thienyl, and cycloalkyl, were used, pyrroles were obtained. A gram-scale preparation experiment and further derivatization of pyridazines demonstrated the potential applicability of our synthesis method. Experimental studies and density functional theory calculations unveiled the origin of the chemoselectivity determining the formation of different products.
首次成功地将简单的市售碘用作高效且具有化学选择性的催化剂，用于β,γ-不饱和腙的氧化环化反应，在温和条件下制备1,6-二氢哒嗪。有趣的是，当使用含有供电子基团（如呋喃基、噻吩基和环烷基）的活性β,γ-不饱和腙化合物时，得到的是吡咯。哒嗪的克级制备实验及其进一步衍生化证明了我们合成方法的潜在适用性。实验研究和密度泛函理论计算揭示了决定不同产物形成的化学选择性的起源。
