钯催化的芳基亚磺酸钠的脱硫Heck偶联反应

Palladium-catalyzed sodium arylsulfinates-involved desulfitative Heck coupling reaction

摘要:

采用六氟锑酸银为添加剂，实现了钯催化的芳基亚磺酸钠与丙烯酸酯在弱极性溶剂中通过脱硫Heck偶联反应合成肉桂酸酯类化合物。通过核磁共振氢谱、核磁共振碳谱和高分辨质谱对产物进行了结构表征。结果表明：六氟锑酸银活化了钯催化剂，促进了甲苯中芳基亚磺酸钠与丙烯酸酯的脱硫Heck偶联反应；在空气氛围下的产物收率比在氧气和氮气氛围下的产物收率高。通过反应机理分析发现：氧气不利于三苯基膦配体参与的钯催化剂的再生过程，但有利于醋酸铜氧化剂的再生过程。

Abstract:

The palladium-catalyzed desulfitation Heck coupling reaction of sodium arylsulfinates with acrylates in weak polar solvent using silver hexafluoroantimonate as additive to synthesize cinnamates was realized. The structures of products were characterized by 1HNMR, 13CNMR and HRMS. The results showed that silver hexafluoroantimonate activated the palladium catalyst and promoted the desulfitation Heck coupling reaction between sodium arylsulfinates and acrylates in toluene. The yields of the products in air atmosphere were higher than those in oxygen or nitrogen atmosphere. The analysis of reaction mechanism revealed that oxygen was not conducive to the triphenylphosphine ligand-involved regeneration process of the palladium catalyst, but was beneficial to the regeneration of copper acetate oxidant.