三甲基氯硅烷催化羟基取代炔丙酮的环异构化反应合成色酮或3-呋喃酮

TMSCl-catalyzed cycloisomerization of hydroxyl-substituted acetylenic ketones for synthesis of chromones or 3-furanones

目的发展一种合成色酮和3-呋喃酮的方法。方法以甲醇为溶剂,在三甲基氯硅烷的催化作用和70℃加热条件下,羟基取代炔丙酮发生环异构化反应合成了色酮和3-呋喃酮化合物。结果在最优反应条件下,各种邻羟基芳基炔丙酮和γ-羟基炔丙酮能以良好到优异的收率分别得到相应的色酮和3-呋喃酮产物。该环异构化反应具有操作简单、官能团耐受性好以及原子经济性等特点。通过核磁共振和高分辨质谱对所获得的产物结构进行了表征分析。结论开发了三甲基氯硅烷催化邻羟基芳基炔丙酮和γ-羟基炔丙酮的环异构化反应,同时简捷有效地合成了色酮和3-呋喃酮衍生物。

Purposes—To develop a metal-free methodology for the synthesis of chromones and 3-furanones.Methods—With trimethylchlorosilane(TMSCl)as the catalyst,hydroxyl-substituted acetylenic ketones as the substrates,chromones and 3-furanones are obtained by the tandem cycloisomerization in methanol at 70℃.Result—Various o-hydroxyaryl orγ-hydroxy acetylenic ketones are subjected to the optimum reaction conditions,giving the corresponding chromones and 3-furanones in good to excellent yields.This tandem cycloisomerization features simple operation,good tolerance and 100%atom-economy.The structures of all the products are characterized and analyzed by nuclear magnetic resonance and high-resolution mass spectrometer.Conclusion—A concise and efficient TMSCl-catalyzed cycloisomerization reaction of o-hydroxyaryl orγ-hydroxy acetylenic ketones is provided herein to obtain chromones and 3-furanones under mild conditions.