金催化炔基膦酸酯水合反应合成β-羰基膦酸酯

Effective Transformation of Alkynylphosphonates into β-Ketophosphonates with a Gold(I) Catalyst

β-羰基膦酸酯是一类重要的有机化合物和反应中间体,在有机合成及药物化学中发挥着重要的作用.提供了一种高原子经济性、高选择性、温和的炔基膦酸酯水合反应体系.实验结果表明:在阳离子金催化剂(2.5 mol%)的催化作用下,以1,2-二氯乙烷(1 m L)为溶剂,室温下炔基膦酸酯(1 mmol)与水(3 mmol)发生水合反应,高收率、高区域选择性地得到β-羰基膦酸酯化合物(收率≥92%).该方法具有底物适用范围广、反应条件温和、环境友好等优点,为含β-羰基膦酸酯结构单元的天然产物及复杂药物分子的合成提供了一种新途径.

β-Ketophosphonates are an important class of carbonyl compounds which exhibit a wide range of biological activities and outstanding metal-complexing abilities. They are building blocks in organic synthesis, especially as intermediates for the synthesis of a,β-unsaturated carbonyl compounds, chrial β-hydroxy and β-hydroxy phosphonic acids. In this paper, a simple, convenient and environmentally benign method to synthesize the β-ketophosphonates from alkynylphosphonates was developed, which can be easily prepared in one step from commercial terminal alkynes. In the presence of 2.5 mol% XPhosAuSbF6 and 3 equiv, of water in dichloroethane at room temperature, a broad range of alkynylphosphonates were converted into the corresponding β-ketophosphonates in nearly equivalent conversion through gold-catalyzed hydration reaction. The presented methodology will provide new strategies for β-ketophosphonates-type natural product and drug synthesis, which has important academic significance and application value.