N-Aminopyridinium reagents as traceless activating groups in the synthesis of N-Aryl aziridines.
N-Aminopyridinium reagents as traceless activating groups in the synthesis of N-Aryl aziridines.
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DOI：
10.1038/s41467-022-31032-w
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发表时间：
2022-06-10
影响因子：
16.6
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中科院分区：
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N-官能化氮杂环丙烷，其既是有用的中间体又是重要的合成目标，可以设想为由氮烯的加成产生（即，NR片段）与烯烃底物的反应。大多数氮烯的特殊反应性，特别是关于单分子分解，阻止氮烯转移到合成N-官能化氮丙啶的一般应用。在这里，我们展示了N-芳基氮丙啶的合成，通过1）烯烃氮丙啶与N-氨基吡啶试剂反应，得到N-吡啶氮丙啶，然后2）N-吡啶氮丙啶与芳基硼酸的Ni催化的C-N交叉偶联。N-吡啶鎓氮丙啶中间体还参与与各种亲核试剂的开环化学反应，以提供1，2-氨基官能化产物。机理研究表明，氮丙啶交叉偶联收益通过一个非典型的机制，涉及初始氮丙啶开放促进的溴抗衡的Ni催化剂，C-N交叉偶联，最后氮丙啶重新关闭。总之，这些结果提供了新的机会，以实现选择性纳入通用芳基氮烯等价物的有机分子。氮杂环丙烷是一种重要的合成中间体。在这里，作者展示了一种基于N-氨基吡啶鎓试剂合成N-芳基氮杂环丙烷的策略，随后是N-吡啶鎓氮杂环丙烷与芳基硼酸的Ni催化的C-N交叉偶联。
N-functionalized aziridines, which are both useful intermediates and important synthetic targets, can be envisioned as arising from the addition of nitrenes (i.e., NR fragments) to olefinic substrates. The exceptional reactivity of most nitrenes, in particular with respect to unimolecular decomposition, prevents general application of nitrene-transfer to the synthesis of N-functionalized aziridines. Here we demonstrate N-aryl aziridine synthesis via 1) olefin aziridination with N-aminopyridinium reagents to afford N-pyridinium aziridines followed by 2) Ni-catalyzed C–N cross-coupling of the N-pyridinium aziridines with aryl boronic acids. The N-pyridinium aziridine intermediates also participate in ring-opening chemistry with a variety of nucleophiles to afford 1,2-aminofunctionalization products. Mechanistic investigations indicate aziridine cross-coupling proceeds via a noncanonical mechanism involving initial aziridine opening promoted by the bromide counterion of the Ni catalyst, C–N cross-coupling, and finally aziridine reclosure. Together, these results provide new opportunities to achieve selective incorporation of generic aryl nitrene equivalents in organic molecules. Aziridines are useful intermediates, present in important synthetic targets. Here, the authors show a strategy for the synthesis of N-aryl aziridines based on N-aminopyridinium reagents followed by Ni-catalyzed C–N cross-coupling of N-pyridinium aziridines with aryl boronic acids.
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