有机化学 ›› 2023, Vol. 43 ›› Issue (12): 4261-4267.DOI: 10.6023/cjoc202306012 上一篇    下一篇

研究论文

硅氨基镧化合物催化合成磷酸烯醇酯

潘康, 徐凡*()   

  1. 苏州大学材料与化学化工学部 苏州 215123
  • 收稿日期:2023-06-15 修回日期:2023-07-13 发布日期:2023-07-27
  • 基金资助:
    江苏省高等学校自然科学研究(18KJA150007)

Lanthanum Silylamide-Catalyzed Synthesis of Enol Phosphates

Kang Pan, Fan Xu*()   

  1. College of Chemistry, Chemical Engineering and Material Science, Soochow University, Suzhou 215123
  • Received:2023-06-15 Revised:2023-07-13 Published:2023-07-27
  • Contact: *E-mail: xufan@suda.edu.cn
  • Supported by:
    Natural Science Foundation of the Jiangsu Higher Education Institutions(18KJA150007)

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[(Me3Si)2N]3La(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.

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

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 [(Me3Si)2N]3La(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.

Key words: enol phosphate, lanthanide silylamide, catalysis, phospha-Brook rearrangement, stereoselectivity