新型手性硫醚-亚磷酰胺配体的设计与应用

Designand Application of A Novel Chiral Thioether-phosphoramidite Ligand

根据模块组合法,设计并合成了一种具有亚磷酰胺结构的硫醚配体,该配体具有原料便宜易得、合成步骤简单、易于修饰和结构稳定等特点。以配体/钯络合物催化的丙二酸二甲酯与1,3-二苯基烯丙基醋酸酯的烯丙基化反应作为模板反应,探究了溶剂和碱对其立体控制的影响。随后探究了中心手性与轴手性的匹配/错配现象以及硫醚片段的空间位阻和电性对反应立体控制的作用。在最佳条件下,产物的对映选择性能够达到-76%ee。

A novel chiral thioether-phosphoramidite ligand was synthesized by modular assemble protocol,which featured with short steps,multiple decorating sites and stable structure.The catalytic activity of ligand/Pd complex was investigated with asymmetric allylic alkylation reaction of rac-1,3-diphenylallyl acetate and dimethyl malonate.The solvent effect and base effect were examined,then the match/mismatch phenomenon of the axial chirality and point chirality was investigated.Finally,the influence of steric hindrance and electronic property of the sulfide motifs on the benchmark reaction were examined.Under the optimal reaction conditions,the target product can be obtained in-76%ee.