Reactivity of Arynes for Arene Dearomatization
Reactivity of Arynes for Arene Dearomatization
复制标题
芳烃脱芳构化的芳烃反应性。
DOI：
10.1021/acs.orglett.8b01466
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发表时间：
2018-07-20
期刊：
影响因子：
5.2
通讯作者：
Lee, Daesung
中科院分区：
文献类型：
--
作者：
Karmakar, Rajdip;Le, Anh;Lee, Daesung
一个前所未有的芳烃介导的脱芳反应被描述。由芳烃磺酰基酰胺系三炔和系四炔生成的芳烃中间体与系三烯和芳烃磺酰基的pi体系反应生成含环己-1,3-二烯的五环和六环框架。密度泛函理论（DFT）计算显示了一种亲核脱芳机理，涉及由芳烃衍生的两性离子中间体。还观察到卤素对环己-1,3-二烯部分的脱芳化效率和阻芳化的新效应。
An unprecedented aryne-mediated dearomatization reaction is described. An aryne intermediate generated from arenesulfonyl ynamide-tethered triynes and tetraynes reacts with both the pi-systems of a tethered alkene and the arenesulfonyl group to generate cyclohexa-1,3-diene-containing pentacyclic and hexacyclic frameworks. Density functional theory (DFT) calculations show a nucleophilic dearomatization mechanism involving a zwitterionic intermediate derived from an aryne. A novel halogen effect on the efficiency of the dearomatization and deterrence of aromatization of the cyclohexa-1,3-diene moiety was also observed.