Department of Chemistry, National Central University , No. 300 Jhong-Da Road, Jhong-li, Taoyuan, Taiwan 32001.
J Org Chem. 2017 Oct 6;82(19):10201-10208. doi: 10.1021/acs.joc.7b01705. Epub 2017 Sep 18.
A one-pot synthesis of thioesters directly from carboxylic acids, N,N'-diphenylthiourea, triethylamine, and primary alkyl halides is described. Microwave-assisted heating and a catalytic amount of 4-(dimethylamino)pyridine (DMAP) further improved the yields. Both aromatic and aliphatic carboxylic acids were converted to the corresponding thioesters, and many functional groups were compatible with this reaction. Several possible reaction intermediates were investigated, and the quaternary ammonium salts, derived from alkyl halides and tertiary amines, were the intermediates to yield thioesters. A new reaction mechanism for this thioesterification is proposed.
本文描述了一种从羧酸、N,N'-二苯基硫脲、三乙胺和伯卤代烷直接一锅合成硫酯的方法。微波辅助加热和催化量的 4-(二甲基氨基)吡啶（DMAP）进一步提高了产率。芳香酸和脂肪酸都能转化为相应的硫酯，许多官能团都能与该反应兼容。还研究了几种可能的反应中间体，并且烷基卤化物和叔胺生成的季铵盐是生成硫酯的中间体。本文提出了这种硫酯化反应的新反应机制。
