Cation Radical-Accelerated Nucleophilic Aromatic Substitution for Amination of Alkoxyarenes.
Cation Radical-Accelerated Nucleophilic Aromatic Substitution for Amination of Alkoxyarenes.
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DOI：
10.1021/acs.orglett.0c01621
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发表时间：
2020-06
期刊：
影响因子：
5.2
通讯作者：
N. Venditto;David A. Nicewicz
中科院分区：
文献类型：
--
作者：
N. Venditto;David A. Nicewicz
亲核芳香取代（SNAr）是芳烃功能化的常用方法；然而，这种类型的反应通常仅限于缺乏电子的芳香族卤化物。在这里，我们描述了一种温和的，不含金属的，阳离子自由基加速的亲核芳香取代（CRA-SNAr），使用一种强效的，高氧化性的吖啶光氧化还原催化剂。各种伯胺亲核试剂可选择性取代芳烃C-O键在各种芳基醚底物上。机制证据也支持所提出的CRA-SNAr通路。
Nucleophilic aromatic substitution (SNAr) is a common method for arene functionalization; however, reactions of this type are typically limited to electron-deficient aromatic halides. Herein, we describe a mild, metal-free, cation-radical accelerated nucleophilic aromatic substitution (CRA-SNAr) using a potent, highly oxidizing acridinium photoredox catalyst. Selective substitution of arene C-O bonds on a wide array of aryl ether substrates was shown with a variety of primary amine nucleophiles. Mechanistic evidence is also presented that supports the proposed CRA-SNAr pathway.