研究生: |
黃思穎 Huang, Szu-Ying |
---|---|
論文名稱: |
一價銠金屬催化氮-對甲苯磺醯基之1,2‐二氫喹啉進行不對稱氫芳基化反應 Rhodium(I)-Catalyzed Asymmetric Hydroarylation of N-Tosyl 1,2-Dihydroquinolines |
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: | 2020 |
畢業學年度: | 108 |
語文別: | 中文 |
論文頁數: | 226 |
中文關鍵詞: | 鏡像選擇性 、一價銠金屬催化 、氫芳基化反應 、1,2‐二氫喹啉 、2H-色原烯 、四芳基硼鈉試劑 、不對稱加成反應 、掌性 、掌性雙環[2.2.1]雙烯配基 |
英文關鍵詞: | enantioselective, Rhodium(I)-catalyzed, hydroarylation, 1,2-dihydroquinolines, 2H-chromenes, sodium tetraarylborates, asymmetric addition, chiral, chiral bicyclo[2.2.1]diene ligands |
DOI URL: | http://doi.org/10.6345/NTNU202000854 |
論文種類: | 學術論文 |
相關次數: | 點閱:125 下載:0 |
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本篇論文探討一價銠金屬試劑與掌性雙環[2.2.1]雙烯配基L2a形成之催化劑,於溫度100 ℃且使用環戊基甲基醚為溶劑,並加入甲醇為添加劑的條件下,催化1,2‐二氫喹啉或2H-色原烯12與四芳基硼鈉13進行不對稱加成反應,得到一系列3號位具芳香基之掌性1,2,3,4-四氫喹啉或3號位具芳香基之掌性色原烷14,產率為10–92%,鏡像超越值為87–99%。此外,利用掌性1,2,3,4-四氫喹啉化合物14mh進行去甲基反應及利用掌性1,2,3,4-四氫喹啉化合物14nn經由宮浦硼酸化 (Miyaura borylation)與氧化反應可合成目標產物雌激素乙型受體促效劑 ((R)-3),前者產率為86%,後者兩個步驟的總產率為52%。
This thesis describes an enantioselective addition of sodium tetraarylborates 13 to 1,2-dihydroquinolines or 2H-chromenes 12 in cyclopentyl methyl ether at 100 ℃ with 5.0 equiv of methanol as an additive in the presence of 3.0 mol % of Rh(I)-catalyst in situ generated from the [RhCl(C2H4)2]2 and chiral bicyclo[2.2.1]heptadiene ligand L2a. The desired products 14 were generated in 10–92% yields with 87–99% ees. In addition, the synthesis of Estrogen receptor β agonist ((R)-3) was achieved by demethylation of compound 14mh in 86% yield. The desired product ((R)-3) was also obtained by Miyaura borylation of compound 14nn followed by oxidation in 52% yield for 2 steps.
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