Synthesis of Benzoisoselenazolones via Rh(III)‐Catalyzed Direct Annulative Selenation by Using Elemental Selenium
Synthesis of Benzoisoselenazolones via Rh(III)‐Catalyzed Direct Annulative Selenation by Using Elemental Selenium
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使用元素硒通过 Rh(III) 催化直接环硒化合成苯并异硒唑啉酮
DOI：
10.1002/chem.202103485
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发表时间：
2021
期刊：
影响因子：
--
通讯作者：
Miura Masahiro
中科院分区：
文献类型：
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作者：
Xu‐Xu Qing‐Feng;Nishii Yuji;Uetake Yuta;Sakurai Hidehiro;Miura Masahiro
异硒唑啉酮衍生物由于其潜在的治疗活性和在有机合成中不可或缺的应用而引起了广泛的研究兴趣。功能化异硒唑酮支架的有效构建仍然具有挑战性，因此具有改进的操作简单性的新合成方法特别令人感兴趣。在这篇手稿中，我们介绍了铑催化的直接硒成环通过使用稳定和易处理的元素硒。在温和的反应条件下，成功地将一系列苯甲酰胺类和丙烯酰胺类化合物与硒偶联，得到的异硒唑酮化合物可作为合成多种有机硒化合物的关键前体。基于设计的对照实验和X射线吸收光谱测量，我们提出了一种前所未有的硒化机制，涉及高度亲电的Se（IV）物种作为反应性硒供体。通过计算研究进一步验证了反应机理。
Isoselenazolone derivatives have attracted significant research interest because of their potent therapeutic activities and indispensable applications in organic synthesis. Efficient construction of functionalized isoselenazolone scaffolds is still challenging, and thus new synthetic approaches with improved operational simplicity have been of particular interest. In this manuscript, we introduce a rhodium‐catalyzed direct selenium annulation by using stable and tractable elemental selenium. A series of benzamides as well as acrylamides were successfully coupled with selenium under mild reaction conditions, and the obtained isoselenazolones could be pivotal synthetic precursors for several organoselenium compounds. Based on the designed control experiments and X‐ray absorption spectroscopy measurements, we propose an unprecedented selenation mechanism involving a highly electrophilic Se(IV) species as the reactive selenium donor. The reaction mechanism was further verified by a computational study.