醋酸银甲醇促进炔基膦酸酯水合制备β-羰基膦酸酯有机化学.pdfVIP

DOI: 10.6023/cjoc201502015 研究论文 有机化学 Chinese Journal of Organic Chemistry ARTICLE 醋酸银/ 甲醇促进炔基膦酸酯水合制备β-羰基膦酸酯 刘开建* 欧金花 欧丽娟 刘宏伟 唐新德 李来丙 胡波年 (湖南工学院材料与化学工程系 衡阳 421002) 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 AgOAc 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. 关键词 炔基膦酸酯; β-羰基膦酸酯化合物; 银催化; 水合反应 Effective Transformation of Alkynylphosphonates into β-Ketophosphonates with a Silver(I) Catalyst Liu, Kaijian* Ou, Jinhua Ou, Lijuan Liu, Hongwei Tang, Xinde Li, Laibing Hu, Bonian (Department of Materials and Chemical Engineering, Hunan Institute of Technology, Hengyang 421002) Abstract β-Ketophosphonates are an important class of carbonyl compounds which exhibit a wide range of biological activi- ties 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