有机化学 ›› 2014, Vol. 34 ›› Issue (10): 2007-2014.DOI: 10.6023/cjoc201404046 上一篇    下一篇

研究论文

金催化炔基膦酸酯水合反应合成β-羰基膦酸酯

刘开建, 刘宏伟, 王文革, 欧丽娟, 王津津, 胡波年   

  1. 湖南工学院材料与化学工程系 衡阳 421002
  • 收稿日期:2014-04-24 修回日期:2014-09-03 出版日期:2014-10-25 发布日期:2014-09-09
  • 通讯作者: 刘开建, 胡波年 E-mail:liukaijian_1982@163.com;hbonian@163.com
  • 基金资助:

    湖南省科技计划(No. 2014FJ3053)、国家自然科学基金(No. 21176061)、湖南省自然科学基金(No. 13JJ3132)、湖南省重点建设学科和衡阳市科技计划资助项目.

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

Liu Kaijian, Liu Hongwei, Wang Wenge, Ou Lijuan, Wang Jingjing, Hu Bonian   

  1. Department of Materials and Chemical Engineering, Hunan Institute of Technology, Hengyang 421002
  • Received:2014-04-24 Revised:2014-09-03 Online:2014-10-25 Published:2014-09-09
  • Supported by:

    Project supported by the Science and Technology Planning Project of Hunan Province (No. 2014FJ3053), the National Natural Science Foundation of China (No. 21176061), the Natural Science Foundation of Hunan Province (No. 13JJ3132), the Construct Program of the Key Discipline in Hunan Province and Science and Technology Planning Project of Hengyang City (No. 2014FJ3053).

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 mL)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.

关键词: 炔基膦酸酯, β-羰基膦酸酯化合物, 金催化, 水合反应

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 α,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.

Key words: alkynylphosphonates, β-ketophosphonate, gold catalysis, hydration reaction