Intramolecular Imino-ene Reaction of Azirines: Regioselectivity, Diastereoselectivity, and Computational Insights
Intramolecular Imino-ene Reaction of Azirines: Regioselectivity, Diastereoselectivity, and Computational Insights
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氮丙啶的分子内亚氨基烯反应：区域选择性、非对映选择性和计算见解
DOI：
10.1021/acs.joc.9b00087
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发表时间：
2019
影响因子：
3.6
通讯作者：
Xu Hua-Dong
中科院分区：
文献类型：
--
作者：
Shen Mei-Hua;Qu Hong-Yu;Dai Ping;Zhou Hao;Liu Tai-Shang;Bao Xiaoguang;Xu Defeng;Xu Hua-Dong
对2 H-氮丙啶的分子内亚胺-烯反应进行了实验和计算研究，结果表明：（1）该协同反应是在烯烃的E-CH基团上区域选择性地进行的，（2）N-连接基的几何构型对反应活化能和非对映选择性有显著影响，以锥型烷基胺为连接基时，得到了唯一的顺式产物;（3）当反应必须与Z-CH基团发生时，无论N-键的性质如何，只观察到顺式-非对映选择性。
Intramolecular imino-ene reaction of 2H-aziridine has been studied experimentally and computationally, demonstrating that (1) the concerted process takes place regioselectively on the alkeneE-CH group; (2) the geometry of the N-linker impacts the reaction activation energy and diastereoselectivity significantly, with pyramidal alkyl amine as the linkage, an exclusivecis-product is achieved; (3) when the reaction has to occur with theZ-CH group, thecis-diastereoselectivity is solely observed regardless of the nature of the N-linkage.