醋酸银/甲醇促进炔基膦酸酯水合制备β-羰基膦酸酯  

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

作　　者：刘开建[1] 欧金花 欧丽娟[1] 刘宏伟[1] 唐新德[1] 李来丙[1] 胡波年[1] 

机构地区：[1]湖南工学院材料与化学工程系,衡阳421002

出　　处：《有机化学》2015年第9期1889-1896,共8页Chinese Journal of Organic Chemistry

基　　金：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;衡阳市科技计划(No.2014KJ26)资助项目~~

摘　　要：报道了一种高原子经济性、高选择性合成β-羰基膦酸酯类化合物的催化水合体系.实验发现以廉价的Ag OAc作为催化剂,甲醇作为助催化剂,炔基膦酸酯顺利发生水合反应生成相应的目标产物,产率优秀.反应无需惰性气体保护,具有良好的官能团耐受性,杂环、卤素等官能团及杂环体系都对反应无明显影响.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, chiral β-hydroxy and β-hydroxy phosphonic acids. In this paper, a cheap, 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 10 mol% AgOAc and 4 equiv. of water in methanol at 110 ℃, a broad range of alkynylphosphonates were converted into the corresponding β-ketophosphonates in nearly equivalent conversion through silver/methanol-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.

关 键 词：炔基膦酸酯 β-羰基膦酸酯化合物 银催化 水合反应 

分 类 号：O627.51[理学—有机化学]