School of Chemistry and Chemical Engineering, Key Laboratory of the Colloid and Interface Chemistry, Ministry of Education, Shandong University, Jinan, 250100, China.
College of Chemistry and Chemical Engineering, Key Laboratory of Special Function Materials and Structure Design of Ministry of Education, Lanzhou University, Lanzhou, 730000, China.
Nat Commun. 2022 Jun 22;13(1):3563. doi: 10.1038/s41467-022-31293-5.
The activation of aziridines typically involves the use of strong Lewis acids or transition metals, and methods relying on weak interactions are rare. Herein, we report that cooperative chalcogen bonding interactions in confined sites can activate sulfonyl-protected aziridines. Among the several possible distinct bonding modes, our experiments and computational studies suggest that an activation mode involving the cooperative Se···O and Se···N interactions is in operation. The catalytic reactions between weakly bonded supramolecular species and nonactivated alkenes are considered as unfavorable approaches. However, here we show that the activation of aziridines by cooperative Se···O and Se···N interactions enables the cycloaddition of weakly bonded aziridine-selenide complex with nonactivated alkenes in a catalytic manner. Thus, weak interactions can indeed enable these transformations and are an alternative to methods relying on strong Lewis acids.
氮丙啶的活化通常涉及使用强路易斯酸或过渡金属，而依赖弱相互作用的方法则很少见。在此，我们报告说，在封闭的场所中，协同的硫属键相互作用可以活化磺酰基保护的氮丙啶。在几种可能的不同键合模式中，我们的实验和计算研究表明，涉及协同 Se···O 和 Se···N 相互作用的活化模式在起作用。弱键合超分子物种与非活化烯烃之间的催化反应被认为是不利的方法。然而，在这里我们表明，通过协同 Se···O 和 Se···N 相互作用的活化可以使弱键合的氮丙啶-硒化物配合物与非活化烯烃以催化方式进行环加成。因此，弱相互作用确实可以实现这些转化，并且是替代依赖强路易斯酸的方法的一种选择。
