Author: |
王得至 Wang, De-Chih |
---|---|
Thesis Title: |
經由不對稱有機連鎖1,6/1,4-加成反應合成雙環[3.3.1]壬-9-酮架構 Asymmetric Synthesis of Bicyclo[3.3.1]nonan-9-one Skeletons via Organocascade 1,6/1,4-Addition Sequence |
Advisor: |
陳焜銘
Chen, Kwun-Min |
Degree: |
碩士 Master |
Department: |
化學系 Department of Chemistry |
Thesis Publication Year: | 2016 |
Academic Year: | 104 |
Language: | 中文 |
Number of pages: | 138 |
Keywords (in Chinese): | 去對稱化 、有機連鎖反應 、1,6-加成反應 、雙環[3.3.1]壬-9-酮 |
Keywords (in English): | Desymmetrization, Organocascade, 1,6-addition, Bicyclo[3.3.1]nonan-9-one |
DOI URL: | https://doi.org/10.6345/NTNU202203819 |
Thesis Type: | Academic thesis/ dissertation |
Reference times: | Clicks: 122 Downloads: 1 |
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利用有機小分子進行連鎖催化反應,為有效率之有機合成策略,另一方面,不對稱有機催化1,6-加成反應則較具挑戰。使用二烯化合物搭配環己酮的去對稱化反應,進行不對稱有機連鎖1,6-加成反應,可得到良好產率及優異立體選擇性的產物。
本文利用4-甲基環己酮114a為手性前驅起始物,在L-脯胺酸所衍生之有機催化劑I的作用下,與1,3-茚二酮所衍生的二烯化合物104,於室溫下進行1,6加成/1,4加成連鎖反應。得到以雙環[3.3.1]壬-9-酮為主體架構之產物115,產率45% - 99%,非鏡像選擇性> 20:1,鏡像選擇性最高達97% ee。
Organocascade reaction that catalyzed by organic small molecules is an efficient strategy for organic synthesis, on the other hand, asymmetric organocatalytic 1,6-addition cascade reactions are still a challenge.
In this study, the addition of prochiral 4-methyl cyclohexanone to diene-tethered indan-1,3-dione proceeded in asymmetric 1,6/1,4-addition manner to give the bicyclo[3.3.1]nonan-9-one products in good yields and with excellent stereoselectivity. The bridged bicyclic products 115 were obtained in 45-99% yields and with excellent stereoselectivities (up to > 20:1 dr and up to 97% ee).
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