林文偉Lin, Wen-Wei黃炫瑞Huang, Xuan-Rui2023-12-089999-12-312023-12-082023https://etds.lib.ntnu.edu.tw/thesis/detail/543a72134848ff3c3ca2bc5583e51511/http://rportal.lib.ntnu.edu.tw/handle/20.500.12235/121015過去幾十年中，膦催化反應因在有機合成中提供了一種強大且無金屬的碳-碳鍵建構方法而受到廣泛關注。自 Trost 教授和陸熙炎教授發表的開創性工作報導以來，聯烯酸酯和炔酸酯被認為是這個領域中最多用途的反應物。在所有電子不足的烯烴中，其中對γ-乙烯基炔酸酯的膦催化反應的研究仍在探索階段。在本研究中，我們使用γ-乙烯基炔酸酯和3-高醯基香豆素作為起始物，對兩者的化學選擇性的1,4-/1,7-加成反應，生成取代的二烯酸酯進行一系列的研究。在沒有添加酸性添加劑時，膦催化劑能夠促進 3-高醯基香豆素對γ-乙烯基炔酸酯的1,4-加成反應。當在反應中使用苯酚作為添加劑時，我們發現它能夠影響γ-乙烯基炔酸酯的加成反應位置，然後選擇性地生成1,7-加成產物。此外，通過親核性三級胺的催化也可以獲得1,4-加成產物。本文報導了一種奎寧衍生的硫脲催化的不對稱雙環化策略，使用亞烷基米氏酸作為受體-供體-受體與鄰位羥基偶氮甲基亞胺依序進行不對稱催化的 (3+2) 環加成/酯轉換/脫羧反應。儘管在低催化量下，也可以在室溫下以優異的反應效率以及優異的產率合成出具有良好鏡像選擇性的 chromeno[4,3-b]pyrrolidines 產物。此外，根據控制實驗，提出了一種合理的活化模型，該模型認為奎寧衍生的硫脲催化劑與亞烷基米氏酸結構之間的氫鍵作用對於優異的立體誘導起到重要作用。Phosphine-catalyzed reactions have gained attention in organic synthesis for their metal-free approach to carbon-carbon bond formation. Alkynoates and allenoates are versatile substrates in this field. Our study focused on the phosphine-catalyzed reactions of γ-vinyl alkynoates.We investigated the chemoselective 1,4-/1,7-addition reactions between γ-vinyl alkynoates and 3-homoacyl coumarins, leading to substituted dienoates. The phosphine catalyst promoted 1,4-addition of 3-homoacyl coumarins to γ-vinyl alkynoates without acidic additives. By adding phenol as an additive, we observed selective 1,7-addition products. Additionally, 1,4-addition products could be obtained with catalytic nucleophilic tertiary amines or by adjusting the reaction solvent with acidic additives.We developed an asymmetric double annulation strategy using alkylidene Meldrum's acid as an acceptor-donor-acceptor with o-hydroxyl azomethine ylide. The methodology involves a (3+2) cycloaddition/esterification/decarboxylation sequence. Efficient synthesis of chromeno[4,3-b]pyrrolidines is achieved at room temperature with high yields, excellent reaction efficiency, and enantioselectivity, utilizing a low catalyst loading. The activation model suggests the significance of hydrogen bonding between the quinine-derived thiourea catalyst and alkylidene Meldrum's acid motif for achieving outstanding stereoselectivity, supported by controlled experiments.膦催化14-/17-加成添加劑效應不對稱合成亞烷基米氏酸γ-乙烯基炔酸酯化學選擇性Phosphine-Catalyzed 14-/17-AdditionAdditive EffectsAsymmetry SynthesisAlkylidene Meldrum's Acidchromeno[43-b]pyrrolidinesγ-Vinyl AlkynoatesChemoselectivityetd