研究生: |
黃普航 Huang, Pu-Hang |
---|---|
論文名稱: |
一價銠金屬/雙環[2.2.1]雙烯配基催化烯醇醚基三氟硼酸鉀鹽與芳香基亞胺進行不對稱加成反應及藥物(S)-達伯西汀的合成應用 Rhodium/Chiral Diene-catalyzed Enantioselective Addition of Potassium Enol Ether Trifluoroborates to N-Tosyl Aldimines: Synthesis of (S)-Dapoxetine |
指導教授: |
吳學亮
Wu, Hsyueh-Liang |
學位類別: |
碩士 Master |
系所名稱: |
化學系 Department of Chemistry |
論文出版年: | 2016 |
畢業學年度: | 104 |
語文別: | 中文 |
論文頁數: | 199 |
中文關鍵詞: | 達伯西汀 、一價銠金屬 、三氟硼酸鉀鹽 、掌性 、烯丙基胺 、不對稱催化 |
英文關鍵詞: | Dapoxetine, Potassium trifluoroborates, allylic amine, diene ligand |
DOI URL: | https://doi.org/10.6345/NTNU202204538 |
論文種類: | 學術論文 |
相關次數: | 點閱:200 下載:0 |
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本論文利用一價銠金屬與本實驗室開發之掌性雙環[2.2.1]雙烯配基L1e的催化系統,使各式烯醇醚基三氟硼酸鉀鹽試劑 53a‒f與芳香基亞胺10a‒o進行不對稱催化加成反應,在100 oC下以甲苯作為溶劑,添加100 wt%研磨過分子篩 (MS 4Å),反應六小時,可合成出具有高鏡像選擇性的新型掌性烯丙基胺骨架之產物34,其產率為21%到83%,鏡像超越值為94%到>99.5% ee。
在合成應用上,利用合成出的新型掌性烯丙基胺化合物34ae,經由簡單的官能基轉變,就可以合成出市售藥物 (S)-Dapoxetine (60)。
This thesis describes the asymmetric synthesis of optically active amines bearing enol ethers.
In the presence of 5.0 mol% of the Rh(I) catalyst comprising chiral diene ligand L1e, the enantioselective addition of potassium enol ether trifluoroborates (53a‒f) to aldimines bearing N-Ts protecting groups afforded the desired allylic amines in 21– 83% yields with 94–>99.5% ee.
The method was applied to the total synthesis of (S)-Dapoxetine (60).
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