- 學位論文
N-保護-3-硝基吲哚和2-氨基苯扎丙酮的不對稱有機催化形式 [4+2] 環加成反應
Asymmetric Organocatalytic Formal [4+2] Cycloaddition of N-protected-3-Nitroindoles and 2-Aminobenzalacetones
若您是本文的作者，可授權文章由華藝線上圖書館中協助推廣。
摘要
近年來，發現一些具有生物活性的天然物，都有著四氫-5H-吲哚并[2,3-b]喹啉的核心骨架。過去的文獻中，對於此類架構合成必須透過金屬催化劑控制立體選擇性，直接使用3-硝基吲哚搭配不對稱有機催化方法尚未被發表。本研究首次展示透過不對稱有機催化形式[4+2]環加成反應，構建四氫-5H-吲哚并[2,3-b]喹啉衍生物。 使用雙功能金雞納生物鹼方醯胺催化劑，對3-硝基吲哚和甲基-2-(甲苯磺酰氨基)苯基α,β-不飽和酮，在溫和的反應條件下，進行鏡像選擇性有機催化反應，合成一系列含有三個連續立體中心的四氫-5H-吲哚并[2,3-b]喹啉衍生物，得到良好的產率（高達60%）和高度立體選擇性（高達15:1 dr和98% ee）。
並列摘要
In recent years, some biologically active natural products have been found to have the core skeleton of tetrahydro-5H-indolo[2,3-b]quinoline. In the past literature, the stereoselectivity must be controlled by metal catalysts for this type of architecture synthesis, and the direct use of 3-nitroindole with asymmetric organocatalysis methods has not been published. This study features the first asymmetric organocatalytic formal for constructed tetrahydro-5H-indolo[2,3-b]quinolines derivatives. An organocatalytic enantioselective synthesis of tetrahydro-5H-indolo[2,3-b]quinolines derivatives was demonstrated using 3-nitroindoles and methyl 2-(tosylamino)phenyl α,β-unsaturated ketones in the presence of the bifunctional cinchona alkaloids squaramide catalyst. A series of tetrahydro-5H-indolo[2,3-b]quinolines derivatives containing three continuous stereogenic centers were obtained in good yields (up to 60%) and with high stereoselectivities (up to 15:1 dr and up to 98% ee).
參考文獻
1. Chirality (chemistry). https://en.wikipedia.org/wiki/Chirality_(chemistry).
2. Stereoisomerism. https://en.wikipedia.org/wiki/Stereoisomerism.
3. Leitereg, T. J.; Guadagni, D. G.; Harris, J.; Mon, T. R.; Teranishi, R. Chemical and Sensory Data Supporting the Difference between the Odors of the Enantiomeric Carvones. J. Agr. Food. Chem. 1971, 19 (4), 785-787.
4. Friedman, L.; Miller, J. G. Odor Incongruity and Chirality. Science 1971, 172 (3987), 1044-1046.
5. Enantiopure Drug. https://en.wikipedia.org/wiki/Enantiopure_drug.
延伸閱讀
- 呂家豪（2021）。N-亞柳白胺酸衍生之手性氧釩錯合物催化烯烴的分子間不對稱1,2-和1,4-氧化三氟甲基化反應〔碩士論文，國立清華大學〕。華藝線上圖書館。https://www.airitilibrary.com/Article/Detail?DocID=U0016-2412202116191579
- 蔡佩玲（2009）。2-(6-取代-3(Z)-己烯-1,5-雙炔)硝基苯之合成與生物活性探討〔碩士論文，高雄醫學大學〕。華藝線上圖書館。https://www.airitilibrary.com/Article/Detail?DocID=U0011-3101200918564100
- 陳家玄（2021）。催化1,3-二烯烴進行[2+2]-亞硝基芳香烴環化加成反應和[3+2]-α-重氮酮環化反應〔碩士論文，國立清華大學〕。華藝線上圖書館。https://www.airitilibrary.com/Article/Detail?DocID=U0016-0209202114085299
- Wang, Z. (2012). Organocatalytic asymmetric synthesis of dihydrodibenzofurans and asymmetric aziridination of α-nitroalkenes [doctoral dissertation, The University of Hong Kong]. Airiti Library. https://www.airitilibrary.com/Article/Detail?DocID=U0029-0511201300009007
- 楊芷羚（2020）。Highly Diastereoselective Synthesis of 2,3,4,5-Tetrasubstituted Pyrrolidines via Organocatalytic [3+2] Cycloaddition〔碩士論文，國立臺灣師範大學〕。華藝線上圖書館。https://doi.org/10.6345/NTNU202001019