铱催化的醋酸盐与伯醇和二醇的α-烷基化反应。

Iridium-catalyzed alpha-alkylation of acetates with primary alcohols and diols.

机构信息

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.

出版信息

J Am Chem Soc. 2010 Mar 3;132(8):2536-7. doi: 10.1021/ja9106989.

DOI:10.1021/ja9106989

PMID:20131900

Abstract

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.

摘要

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。