Structure and Reactivity of Aromatic Radical Cations Generated by FeCl3
Structure and Reactivity of Aromatic Radical Cations Generated by FeCl3
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DOI：
10.1021/jacs.8b12827
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发表时间：
2019-02-06
影响因子：
15
通讯作者：
Ishihara, Kazuaki
中科院分区：
文献类型：
--
作者：
Horibe, Takahiro;Ohmura, Shuhei;Ishihara, Kazuaki
本文介绍了由FeCl 3产生的芳香族自由基阳离子的分离和表征。X-射线晶体学分析和动力学研究揭示了芳族自由基阳离子的产生机制。在固态下，观察到自由基阳离子与FeCl 4-的紧密离子对。利用自由基阳离子-FeCl 4-离子对的有效生成，我们探索了由催化量的FeCl 3引发的自由基阳离子诱导的反式茴香脑环加成反应。[4+2]环加成反应和[2+2]环加成反应的底物范围也很广。此外，100克规模的反应证明了使用1摩尔%的FeCl 3作为一个简单的和高活性的引发剂。
This paper describes the isolation and characterization of an aromatic radical cation generated by FeCl3. X-ray crystallographic analysis and kinetic studies reveal the mechanism of the generation of aromatic radical cation. In the solid state, a tight ion-pair of a radical cation with FeCl4- is observed. Leveraging the efficient generation of the radical cation-FeCl4- ion pair, we explore a radical cation-induced cycloaddition of trans-anethole initiated by catalytic amount of FeCl3. Both [4+2] cycloaddition and [2+2] cycloaddition with a broad substrate scope are also described. Moreover, a 100 g-scale reaction is demonstrated with the use of 1 mol % of FeCl3 as a simple and a highly active initiator.