铁催化过氧化氢氧化端炔合成羧酸类化合物

Iron-Catalyzed Oxidative Cleavage of Terminal Alkynes to Carboxylic Acids with Hydrogen Peroxide

报道了一种简单铁盐催化过氧化氢氧化断裂端炔合成羧酸的方法.以4-氯苯乙炔(1a)作为模板底物,采用过氧化氢为氧化剂,探究不同铁催化剂、促进剂、溶剂、温度对羧酸产率的影响.研究结果表明:FeCl2为催化剂、过氧化氢为氧化剂、冰醋酸为促进剂、乙腈-水(3∶1)为溶剂、温度为50℃时是最优反应条件.在此基础上,探究不同炔类化合物对该反应体系的适应性.结果表明:苯乙炔类化合物氧化裂解生成羧酸的产率较高,和官能团相容性好.对反应机理也进行了初步的研究.

An iron-catalyzed oxidative cleavage of alkynes to corresponding carboxylic acids with hydrogen peroxide as oxidant is reported. Using 4-chlorophenylacetylene(1 a)as model substrate to optimize reaction conditions shows that optimal result can be obtained with FeCl2 as the catalyst,H2O2 as the oxidant,and acetic acid as the promoter in acetonitrile-water(3∶1)at 50 ℃. Under the optimized reaction conditions,a variety of acetylene compounds have been examined. Terminal arylalkynes provide superior yields with broad functional group compatibility. Preliminary Mechanistic studies have also been preformed.