Sulfenate Anion Catalyzed Diastereoselective Synthesis of Aziridines
Sulfenate Anion Catalyzed Diastereoselective Synthesis of Aziridines
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硫酸根阴离子催化非对映选择性合成氮丙啶
DOI：
10.1002/anie.202303069
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发表时间：
2023
期刊：
影响因子：
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通讯作者：
Walsh, Patrick J.
中科院分区：
文献类型：
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作者：
Zheng, Zhipeng;Pu, Youge;Adrio, Javier;Walsh, Patrick J.
氮杂环丙烷在有机化学和药物化学中是非常有价值的合成靶标。然而，具有广泛底物范围和良好的非对映选择性的有机催化合成这类结构的情况很少见。在这里，我们报道了一种广泛适用的非对映选择性的合成方法，以亚胺和苯基或烷基卤化物为原料，以亚磺酸阴离子(PHSO-)为催化剂合成反式-氮杂环丙烷。含有杂环芳基、烷基以及富电子和贫电子芳基的底物被证明与该方法兼容(33个 实例)，提供了良好的产率和高的非对映选择性(反式：顺式和gt；20 ： 1)。通过开环反应进一步实现了含环丙基或环丁基的氮杂环丙烷的官能化，通过四步合成得到了环丁基取代的去麻黄碱衍生物。我们提出了一个涉及亚胺可逆加成的机理建议，以解释高的反式非对映选择性。
Aziridines are highly valued synthetic targets in organic and medicinal chemistry. The organocatalytic synthesis of such structures with broad substrate scope and good diastereoselectivity, however, is rare. Herein, we report a broadly applicable and diastereoselective synthetic method for the synthesis oftrans‐aziridines from imines and benzylic or alkyl halides utilizing sulfenate anions (PhSO–) as the catalyst. Substrates bearing heterocyclic aromatic groups, alkyl, and electron‐rich and electron‐poor aryl groups were shown to be compatible with this method (33 examples), giving good yields and high diastereoselectivities (trans:cis>20 : 1). Further functionalization of aziridines containing cyclopropyl or cyclobutyl groups was achieved through ring‐opening reactions, with a cyclobutyl‐substituted norephedrine derivative obtained through a four‐step synthesis. We offer a mechanistic proposal involving reversible addition of the deprotonated benzyl sulfoxide to the imine to explain the hightrans‐diastereoselectivity.