基于末端炔烃一锅法合成取代噻吩和呋喃化合物

One-Pot Synthesis of Substituted Thiophene and Furan Derivatives from Terminal Alkynes

噻吩和呋喃衍生物是许多天然产物、药物和发光材料的核心骨架,因此发展一种从简单易得的原料高效合成呋喃和噻吩衍生物的方法具有非常重要的应用价值.该研究实现了一锅法高产率合成2,5-二取代呋喃、2,5-二取代噻吩、苯并呋喃和苯并噻吩化合物.首先通过铜催化末端炔烃Glaser偶联反应合成1,4-二取代丁二炔化合物,接着硫化钠(氢氧化钾)参与水解和环化反应得到2,5-二取代噻吩和呋喃化合物.该合成策略同样适用于合成苯并呋喃和苯并噻吩化合物,通过末端炔与邻氟碘苯的Sonogashira偶联反应,然后硫化钠(或氢氧化钾)参与碳氟键的水解和环化反应得到相应的苯并噻吩和苯并呋喃化合物.该合成方法具有反应条件温和、操作简便和高产率等优点,可为该类呋喃和噻吩的合成提供简便的途径.

The development of efficient and sustainable methods for the synthesis of thiophene and furan derivatives is an important task because of the central role of this class of compounds in many natural products, pharmaceuticals and designed materials applications. In this work, a highly efficient selective synthesis of 2,5-disubstituted furan, 2,5-disubstituted thiophene derivatives, benzo[b]furan and benzo[b]thiophene derivatives using terminal alkynes has been developed. This one-pot procedure involves C（sp）-C（sp） oxidative coupling reaction, the selective hydration and intramolecular annulation of two C≡C triple bond which is a promising synthetic strategy. Meanwhile, the benzo[b]furan and benzo[b]thiophene derivatives were facilely synthesized via Sonogashira coupling reaction, regioselective C-F bond hydration and annulation process in good yield. This reaction was a convenient and simple pathway for the synthesis of the thiophene or furan derivatives.