Asymmetric Vinylogous Aza-Darzens Approach to Vinyl Aziridines
Asymmetric Vinylogous Aza-Darzens Approach to Vinyl Aziridines
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DOI：
10.1021/acs.orglett.8b02074
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发表时间：
2018-08-17
期刊：
影响因子：
5.2
通讯作者：
Njardarson, Jon T.
中科院分区：
文献类型：
--
作者：
Chogii, Isaac;Das, Pradipta;Njardarson, Jon T.
报道了一种不对称组装顺式乙烯基氮杂环丙烷的新方法。用γ-离去基团修饰的策略性取代的二烯醇酯与手性亚磺酰亚胺反应，以良好至优异的产率得到手性乙烯基氮丙啶产物。这是第一个系统的研究，实现了一个有用的不对称乙烯基氮杂-DarkeneR反应。该反应是由顺式选择性加成引发的，在溴化物置换后得到顺式-乙烯基氮丙啶产物。低的顺式-非对映选择性归因于竞争的逆曼尼希途径。
A new asymmetric approach to assemble cis-vinyl aziridines is reported. A reaction of strategically substituted dienolates, decorated with a gamma-leaving group, with chiral sulfinimines afforded chiral vinyl aziridine products in good to excellent yields. This is the first systematic study toward the realization of a useful asymmetric vinylogous aza-Darzens reaction. The reaction is initiated by a syn-selective addition, affording cis-vinyl aziridine products after displacement of bromide. The low syn-diastereoselectivity is attributed to competing retro-Mannich pathways.