Arene Amination Instead of Fluorination: Substitution Pattern Governs the Reactivity of Dialkoxybenzenes with Selectfluor
Arene Amination Instead of Fluorination: Substitution Pattern Governs the Reactivity of Dialkoxybenzenes with Selectfluor
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DOI：
10.1021/acs.joc.1c00231
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发表时间：
2021-03-31
影响因子：
3.6
通讯作者：
Lectka, Thomas
中科院分区：
文献类型：
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作者：
Capilato, Joseph N.;Lectka, Thomas
众所周知，芳烃取代模式会影响给定转化的区域选择性，但不一定影响反应性的类型。在这里，我们报告了烷氧芳烃的取代模式决定了在与Selectfluor的反应中是假设的单电子还是双电子反应占主导地位。本文介绍了富电子芳烃单电子氧化后直接形成C-H到C-N键的一系列胺化产物。我们证明了这种转化合成医学和生物学相关的氮杂环的能力。最后，用计算化学和竞争实验探讨了这种不寻常的“机械开关”。
Arene substitution patterns are well-known to affect the regioselectivity of a given transformation but not necessarily the type of reactivity. Herein, we report that the substitution pattern of alkoxyarenes dictates whether a putative one-electron or two-electron reaction predominates in reactions with Selectfluor. A series of amination products is presented, resulting from the single-electron oxidation of electron-rich arenes followed by direct C-H to C-N bond formation. We demonstrate the ability of this transformation to synthesize medicinally and biologically relevant nitrogen heterocycles. Lastly, this unusual "mechanistic switch" is probed with computational chemistry and competition experiments.