中文摘要：

β-羰基膦酸酯具有广泛的生物学活性,在著名的Horner-Wadsworth-Emmons（HWE）反应中用于合成α,β-不饱和羰基化合物.为克服现有合成β-羰基膦酸酯类化合物的方法存在的缺陷,在一种无溶剂环境下利用烯烃、亚磷酸酯和氧气为原料,铜/铁共催化氧膦化酯制备β-羰基膦酸酯.结果显示：该反应具有良好的选择性和底物普适性,利用简单易得的起始物料有效地获得一系列β-羰基膦酸酯,并能获得32%-77%的收率.此外,将该反应放大至10克级其收率没有显著下降.进一步利用1H NMR、13C NMR、31P NMR及HRMS等技术对β-羰基膦酸酯化合物进行了结构表征.本研究提供了一种实用、成本低廉、高效、绿色工艺合成β-羰基膦酸酯的方法.图2表2参16

英文摘要：

β-Ketophosphonates are an important class of organic compounds, which attract attention from chemists inacademic and industrial communities due to their wide range of biological activities and significant application in the synthesis of β-unsaturated carbonyl compounds via the well-known Horner-Wadsworttl-Emmons （HWE） reaction. Nevertheless, almost all of the established methods are inevitably accompanied with problems, including the need of extra preparation steps for the active precursors, a lack of functionality tolerance, low atom economy, or the generation of stoichiometric amounts of wastes. Here, we describe a green and economical copper/iron-cocatalyzed oxyphosphorylation ofalkenes with H-phosphonates and dioxygen leading to fl-ketophosphonates under solvent-free conditions, which could conveniently and efficiently produce β-ketophosphonateswith 32-77% yields from readily-available starting materials with high regioselectivity and excellent functional group tolerance. Moreover, the present reaction can be effectively scaled up to 10 gram scale without significant loss of its efficiency. The chemical structure of obtained β-ketophosphonates was fully characterized by HNMR, CNMR, p NMR and HRMS. This reaction provides a practical, cost-effective, efficient, and green approach to produce β-ketophosphonates.