硅氨基镧化合物催化合成磷酸烯醇酯  

Lanthanum Silylamide-Catalyzed Synthesis of Enol Phosphates

作　　者：潘康 徐凡[1] Pan Kang;Xu Fan(College of Chemistry,Chemical Engineering and Material Science,Soochow University,Suzhou 215123)

机构地区：[1]苏州大学材料与化学化工学部,苏州215123

出　　处：《有机化学》2023年第12期4261-4267,共7页Chinese Journal of Organic Chemistry

基　　金：江苏省高等学校自然科学研究(No.18KJA150007)资助项目.

摘　　要：磷酸烯醇酯有重要的应用价值,发展催化的选择性合成磷酸烯醇酯的方法很有意义.以硅氨基镧化合物[(Me_(3)Si)_(2)N]_(3)La(μ-Cl)Li(THF)_(3)催化4-氧代-4-芳基-2-丁烯酸酯和亚磷酸酯的反应,合成了一系列单一cis-构型的磷酸烯醇酯.对机理的研究表明,反应经历了较为少见的[1,4]-phospha-Brook重排.反应的催化剂易得,立体选择性好,为合成cis-构型的磷酸烯醇酯提供了一种有效的新途径.Enol phosphate has important applicative value in many fields.The development of a catalytic and selective method for the synthesis of enol phosphate is of great significance.The reaction of 4-oxo-4-arylbut-2-enoate and diethyl phosphite catalyzed by lanthanum silylamide[(Me_(3)Si)_(2)N]_(3)La(μ-Cl)Li(THF)_(3)is developed,which provides a series of enol phosphates in cis-configuration.Research on the mechanism indicates that the reaction undergoes a relatively rare[1,4]-phospha-Brook rearrangement.The reaction has advantages of ready availability of catalyst and high selectivity for alkenyl configuration,providing an efficient method for the synthesis of enol phosphates.

关 键 词：磷酸烯醇酯 硅氨基稀土化合物 催化 phospha-Brook重排 立体选择性 

分 类 号：O627.51[理学—有机化学]