手性4-膦酸二酯基-3-卤-2(5H)-呋喃酮的合成与结构

Synthesis and Structure of the Novel Chiral 4 - Dialkyloxyphosphonyl - 2(5H) - furanones

手性呋喃酮1a～1b与亚磷酸三酯2a～2b通过串联的不对称Michael加成/分子内Michalis-Arbazov重排反应,得到了含磷官能团的新手性化合物,5-(S)-(l-孟氧基)-4-膦酸二酯基-3-卤素-2(5H)-呋喃酮4a～4d.该反应具有条件温和,产率高(86%～95%),光学纯度单一(d.e.≥98%)的特点.通过元素分析,IR,UV,~1HNMR,^(13)C NMR,MS,[α]_D^(20)波谱分析数据以及X射线四圆衍射数据确定了它们的化学结构和绝对构型.

In this paper, we report that the tandem asymmetric Michael addition/internal Michalis - Arbazov reaction of 1 with nucleophilic trialkylphosphites afforded optically pure 5-(S) - l - menthyloxy - 4 -dialkyloxy- phosphonyl - 3 - halo - 2(5H) - furanones 4a ~ 4d in 86% ~ 95% yield with d. e.≥98% . The optically pure compound 4a ~ 4d were identified on the basis of their analytical data, such as [ a ] 20D , UV, IR,1H NMR, 13 C NMR, MS and elemental analysis. The absolute configuration of the novel chiral phosphorous compound 4b was established by X - ray crystallography.