Department of Chemistry and Materials Engineering, Faculty of Chemistry, Materials and Bioengineering, High Technology Research Center, and ORDIST, Kansai University, Suita, Osaka 564-8680, Japan.
J Am Chem Soc. 2010 Mar 3;132(8):2536-7. doi: 10.1021/ja9106989.
Acetates were successfully alkylated with primary alcohols and alpha,omega-diols in the presence of tert-BuOK under the influence of IrCl(cod). For instance, the reaction of tert-butyl acetate with n-butanol in the presence of tert-BuOK as a base and IrCl(cod) as a catalyst in tert-BuOH at 100 degrees C produced tert-butyl hexanoate in good yield. When the alpha,omega-diol 1,9-nonanediol was employed, di-tert-butyl tridecanoate was obtained. These reactions are the first report of the alkylation of acetates using alcohols as alkylating agents. This method provides a very convenient direct route to carboxylates, which are very important raw materials in organic and industrial chemistry.
醋酸酯在叔丁醇钾的存在下，在[IrCl(cod)]2的影响下，成功地与伯醇和α,ω-二醇发生了烷基化反应。例如，在叔丁醇钾作为碱和[IrCl(cod)]2作为催化剂的存在下，叔丁基醋酸酯与正丁醇在 100℃下反应，在叔丁醇中生成了叔丁基己酸酯，产率很好。当使用α,ω-二醇 1,9-壬二醇时，则得到二-叔丁基十三烷酸酯。这些反应是首次报道使用醇作为烷基化试剂对醋酸酯进行烷基化。该方法为羧酸酯的合成提供了一条非常方便的直接途径，羧酸酯在有机和工业化学中是非常重要的原料。
