通过氮杂氧化烯丙基阳离子与（）-芳基亚苄基苯胺的（3+2）环加成反应合成咪唑烷-4-酮。
Imidazolidin-4-ones via (3+2) cycloadditions of aza-oxyallyl cations onto ()-arylideneanilines.
作者信息
Eyilcim Oznur, Issever Sezin, Ocal Nuket, Gronert Scott, Erden Ihsan
机构信息
Department of Chemistry, Faculty of Arts and Sciences, Yildiz Technical University, Davutpasa Campus, 34220 Esenler-Istanbul, Turkey.
Department of Chemistry Virginia Commonwealth University, 1001 West Main Street, Richmond, Virginia 23284, USA.
出版信息
Tetrahedron Lett. 2018 Oct 10;59(41):3674-3677. doi: 10.1016/j.tetlet.2018.08.056. Epub 2018 Sep 5.
In the course of our studies on the chemistry of oxyallyl species we uncovered a new (3+2) cycloaddition of aza-oxyallyl systems, generated in situ from -benzyloxy-2-chloroamides in the presence of NEt, onto -arylimines yielding imidazolidin-4-ones in moderate to good yields. The cycloadditions are regioselective. Computational modelling using DFT at the M062×/6-311+G** level is in support the observed regioselectivities. Although the path to the imidazolin-4-one is favored, the product is preferred by almost 8 kcal/mol and could be formed by base-catalyzed epimerization. All products were isolated by chromatography and characterized by means of their FTIR, NMR and HRMS data.
在我们对氧烯丙基物种化学的研究过程中，我们发现了一种新的氮杂氧烯丙基体系的（3 + 2）环加成反应。该体系由苄氧基 - 2 - 氯酰胺在三乙胺存在下原位生成，与芳基亚胺反应，以中等至良好的产率生成咪唑烷 - 4 - 酮。这些环加成反应具有区域选择性。使用密度泛函理论（DFT）在M062×/6 - 311 + G**水平上进行的计算建模支持了观察到的区域选择性。尽管生成咪唑啉 - 4 - 酮的路径是有利的，但另一种产物比其更稳定近8千卡/摩尔，并且可以通过碱催化的差向异构化形成。所有产物均通过色谱法分离，并通过傅里叶变换红外光谱（FTIR）、核磁共振（NMR）和高分辨率质谱（HRMS）数据进行表征。
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