How Do Face-to-Face Stacked Aromatic Rings Activate Each Other to Electrophilic Aromatic Substitution?

How Do Face-to-Face Stacked Aromatic Rings Activate Each Other to Electrophilic Aromatic Substitution?
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面对面堆叠的芳香环如何相互激活以实现亲电芳香取代?

DOI:
10.1021/acs.orglett.3c01401
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发表时间:
2023
期刊:
影响因子:
5.2
通讯作者:
Lectka, Thomas
Lectka, Thomas
中科院分区:
化学1区
文献类型:
--
作者:
Kazim, Muhammad;Wang, Muyuan;Vemulapalli, Srini;Nguyen, Phuong Minh;Wang, Yuang;Siegler, Maxime A.;Dudding, Travis;Lectka, Thomas

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我们已经发现,面对面的π-堆叠的芳环显示出通过相邻堆叠环直接影响探针芳环而不是通过形成中继或“三明治复合物”来相互激活亲电芳族取代的倾向。即使当其中一个环通过硝化而失活时,这种活化仍然有效。所得到的二硝化产物显示出以延伸的平行偏移堆叠形式结晶,与基材形成鲜明对比。
We have found that face-to-face π-stacked aromatic rings show the propensity to activate one another toward electrophilic aromatic substitution through direct influence of the probe aromatic ring by the adjacent stacked ring, rather than through the formation of relay or “sandwich complexes.” This activation remains in force even when one of the rings is deactivated through nitration. The resulting dinitrated products are shown to crystallize in an extended parallel offset stacked form, in stark contrast to the substrate.
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