Aza-[3,3]-Claisen enolate rearrangement in vinylaziridines: stereoselective synthesis of mono-, di-, and trisubstituted seven-membered lactams.
Aza-[3,3]-Claisen enolate rearrangement in vinylaziridines: stereoselective synthesis of mono-, di-, and trisubstituted seven-membered lactams.
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DOI：
10.1002/1521-3765(20010105)7:1
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发表时间：
2001-01
期刊：
影响因子：
--
通讯作者：
U. Lindström*;P. Somfai
中科院分区：
文献类型：
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作者：
U. Lindström*;P. Somfai
几种2，3-二取代的乙烯基氮杂环丙烷已被N-酰化，并在-78 ℃下在THF中进行LiHMDS处理。升温至室温后，所得酰胺烯醇化物进行高度立体选择性的[3，3]-σ-转移重排，以良好的产率得到单-、二-和三取代的七元内酰胺。该方法的范围和局限性已通过使用各种取代的乙烯基氮杂环丙烷进行了研究。一个动力学控制的过程中进行的六元船状过渡态组装已被调用来解释立体化学的反应结果。
Several 2,3-disubstituted vinylaziridines have been N-acylated and subjected to LiHMDS in THF at -78 degrees C. Upon warming to room temperature, the resulting amide enolates underwent a highly stereoselective [3,3]-sigmatropic rearrangement to give mono-, di-, and trisubstituted seven-membered lactams in good yields. The scope and limitations of the process have been investigated by using variously substituted vinylaziridines. A kinetically controlled process proceeding through a six-membered boatlike transition state assembly has been invoked to explain the stereochemical outcome of the reaction.