Author: |
陳明良 Chen, Ming-Liang |
---|---|
Thesis Title: |
銠金屬 (I)/ 掌性雙環 [2.2.1] 雙烯配基催化脂肪族酮醯胺之不對稱芳香化反應 Enantioselective Arylation of Aliphatic Ketoamides Catalyzed by Rh(I) /Chiral Bicyclo [2.2.1] Diene Ligands |
Advisor: |
吳學亮
Wu, Hsyueh-Liang |
Degree: |
碩士 Master |
Department: |
化學系 Department of Chemistry |
Thesis Publication Year: | 2017 |
Academic Year: | 105 |
Language: | 中文 |
Number of pages: | 238 |
Keywords (in Chinese): | 掌性雙環 [2.2.1] 雙烯配基 |
Keywords (in English): | Chiral Bicyclo [2.2.1] Diene Ligands |
DOI URL: | https://doi.org/10.6345/NTNU202202005 |
Thesis Type: | Academic thesis/ dissertation |
Reference times: | Clicks: 116 Downloads: 0 |
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本論文敘述利用一價銠金屬與掌性雙環 [2.2.1] 雙烯配基L1d形成錯合物作為催化劑,以甲苯為溶劑、0.5當量的1,4-二氮雜二環 [2.2.2] 辛烷(DABCO)作為添加劑,在60 °C與80 °C條件下,催化芳香基硼酸分別對α-酮酯或脂肪族酮醯胺進行不對稱1,2-加成反應,得到具有掌性中心的三級脂肪族醇酯與三級脂肪族醇醯胺產物。其產率高達93%,鏡像超越值高達95%。
利用已建立的掌性三級醇醯胺,經過兩步的官能基修飾與合環反應後,再進行簡單的水解反應,可合成具有藥物活性VLA-4 antagonists前驅物4。
In this thesis, a highly enantioselective rhodium-catalyzed 1,2-addition of aryl boronic acids to aliphatic α-ketoesters and aliphatic ketoamides using Rh-catalyst comprising of a chiral bicyclic [2.2.1] diene ligand L1d is described. This transformation provides chiral tertiary alcohol products with up to 93% yield and 95% ee, product 84 is used for the concise synthesis of the VLA-4 antagonists intermediate.
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