| 新型手性硫醚-亚磷酰胺配体的设计与应用 |
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| 引用本文： | 冯彬,林瑶,林舒妤,彭丽燕,张雪莲,游歌云. 新型手性硫醚-亚磷酰胺配体的设计与应用[J]. 合成化学, 2023, 31(1): 23-32. DOI: 10.15952/j.cnki.cjsc.1005-1511.22009 |
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| 作者姓名： | 冯彬 林瑶 林舒妤 彭丽燕 张雪莲 游歌云 |
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| 作者单位： | 百色学院 化学与环境工程学院 桂西区域污染与治理广西高校重点实验室，广西 百色 533000 |
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| 基金项目： | 国家自然科学基金资助项目（21901009）; 广西省自然科学基金资助项目（2019GXNSFBA245075）; 广西中青年教师基础能力提升项目（2019KY0734）; 广西一流学科建设项目（农业资源与环境）资助 |
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| 摘 要： | 根据模块组合法原理，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、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、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。
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| 关 键 词： | 配体设计 手性硫醚 亚磷酰胺 不对称催化 烯丙基化 合成 立体控制 |
| 收稿时间： | 2022-02-07 |
Design and Application of A Novel Chiral Thioether-phosphoramidite Ligand |
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| Feng Bin,LIN Yao,LIN Shuyu,PENG Liyan,ZHANG Xuelian,YOU Geyun. Design and Application of A Novel Chiral Thioether-phosphoramidite Ligand[J]. Chinese Journal of Synthetic Chemistry, 2023, 31(1): 23-32. DOI: 10.15952/j.cnki.cjsc.1005-1511.22009 |
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| Authors: | Feng Bin LIN Yao LIN Shuyu PENG Liyan ZHANG Xuelian YOU Geyun |
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| Affiliation: | Key Laboratory of Regional Ecological Environment Analysis and Pollution Control of West Guangxi, College of Chemistry and Environment Engineering, Baise University, Baise 533000, China |
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| Abstract: | 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. |
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| Keywords: | ligand design chiral thioether chiral phosphoramidite asymmetric catalysis allylic alkylation synthesis stereocontrol |
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