College of Chemistry & Environmental Science, Key Laboratory of Medicinal Chemistry, and Molecular Diagnosis of the Ministry of Education, Key Laboratory of Chemical Biology of Hebei Province, Hebei University, 180 Wusi Donglu, Baoding 071002, P. R. China.
J Org Chem. 2022 Dec 16;87(24):16578-16591. doi: 10.1021/acs.joc.2c02252. Epub 2022 Nov 30.
Amines, especially those with multi-nitrogen moieties, are widespread in natural products and biologically active compounds. Thus, the development of direct and efficient methods to introduce multiple nitrogen-containing fragments into compounds in one step is highly desirable yet challenging. Herein, we report an NIS-promoted selective amino-diazidation and amino-iodoazidation of -homoallyl benzimidates with NaN. By using this protocol, a variety of vicinal diazido-substituted 1,3-oxazines and vicinal iodoazido-substituted 1,3-oxazines were directly synthesized in a controllable manner. Preliminary mechanistic investigations revealed that the reaction operates through a NIS-promoted four-step cascade process. The developed method has the merits of metal-free, excellent functional group compatibility, simple operation, and mild conditions.
胺类，特别是那些具有多氮原子的胺类，广泛存在于天然产物和生物活性化合物中。因此，开发直接、高效的方法将多个含氮片段一步引入化合物中是非常理想的，但也是具有挑战性的。在此，我们报告了 NIS 促进的 -homoallyl 苯并咪唑与 NaN 的选择性氨二氮取代和氨碘氮取代。通过使用该方案，可以以可控的方式直接合成各种邻二氮取代的 1,3-恶嗪和邻碘氮取代的 1,3-恶嗪。初步的机理研究表明，反应通过 NIS 促进的四步级联过程进行。所开发的方法具有无金属、良好的官能团兼容性、操作简单和条件温和的优点。
