Etherification via Aromatic Substitution on 1,3-Disubstituted Benzene Derivatives
Etherification via Aromatic Substitution on 1,3-Disubstituted Benzene Derivatives
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1,3-二取代苯衍生物的芳香取代醚化
DOI：
10.1021/acs.joc.1c02670
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发表时间：
2022
期刊：
影响因子：
--
通讯作者：
Ishizuka Tadao
中科院分区：
文献类型：
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作者：
Tsuzaki Marina;Ando Shin;Ishizuka Tadao
在这项研究中，我们开发了一种通过在存在于另一个吸电子基团（EWG）间位的吸电子基团（EWG）的同位上进行芳香取代来进行醚化的方法。为了提高取代反应的反应性，我们将在四氢呋喃（THF）中的at-BuOK溶液添加到芳香族底物、醇类亲核试剂和18-冠-6-醚在二甲基甲酰胺（DMF）中的混合物中，这被证明是特别有效的序列。在我们建立的条件下，难以用于取代反应的芳族底物，例如用溴化物或氯化物取代基活化的芳基氟化物，在25 °C下适当地转化为相应的醚产物。该反应将潜在地用于通过使用残余的溴化物或氯化物取代基的进一步化学转化将醇连接到另外的官能团。
In this study, we developed a method for etherification via aromatic substitution at the ipso-position of an electron-withdrawing group (EWG) that exists at the meta-position of another EWG. To heighten the reactivity of the substitution reaction, we added at-BuOK solution in tetrahydrofuran (THF) to a mixture of an aromatic substrate, an alcoholic nucleophile, and 18-crown-6-ether in dimethylformamide (DMF), which proved to be a particularly effective sequence. Under the conditions we established, aromatic substrates that are difficult to use for substitution reactions such as aryl fluorides activated with either a bromide or a chloride substituent were aptly converted to corresponding ether products at 25 °C. This reaction would potentially be useful to link an alcohol to an additional functional group through further chemical transformations via the use of a residual bromide or chloride substituent.