Xia Shanghua, Gan Lu, Wang Kailiang, Li Zheng, Ma Dawei
Interdisciplinary Research Center on Biology and Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences , 345 Lingling Lu, Shanghai 200032, China.
J Am Chem Soc. 2016 Oct 19;138(41):13493-13496. doi: 10.1021/jacs.6b08114. Epub 2016 Oct 5.
The combination of Cu(acac) and N,N'-bis(4-hydroxyl-2,6-dimethylphenyl)oxalamide (BHMPO) provides a powerful catalytic system for hydroxylation of (hetero)aryl halides. A wide range of (hetero)aryl chlorides bearing either electron-donating or -withdrawing groups proceeded well at 130 °C, delivering the corresponding phenols and hydroxylated heteroarenes in good to excellent yields. When more reactive (hetero)aryl bromides and iodides were employed, the hydroxylation reactions completed at relatively low temperatures (80 and 60 °C, respectively) at low catalytic loadings (0.5 mol % Cu).
Cu(acac)与N,N'-双(4-羟基-2,6-二甲基苯基)草酰胺(BHMPO)的组合为(杂)芳基卤化物的羟基化提供了一种强大的催化体系。一系列带有供电子或吸电子基团的(杂)芳基氯化物在130°C下反应良好，以良好至优异的产率得到相应的酚类和羟基化杂芳烃。当使用反应活性更高的(杂)芳基溴化物和碘化物时，羟基化反应在相对较低的温度下(分别为80°C和60°C)、低催化负载量(0.5 mol% Cu)下即可完成。
