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Author: 王韻婷
Wang, Yun-Ting
Thesis Title: 一價銠金屬催化有機硼酸與掌性環戊烯酮進行共軛加成反應合成前列腺素衍生物
Rh(I)-Catalyzed Conjugate Addition Reaction of Organoboronic Acids with a Chiral Cyclopentenone for the Synthesis of Prostaglandin Derivatives
Advisor: 吳學亮
Wu, Hsyueh-Liang
Degree: 碩士
Master
Department: 化學系
Department of Chemistry
Thesis Publication Year: 2016
Academic Year: 104
Language: 中文
Number of pages: 148
Keywords (in Chinese): 銠金屬共軛加成前列腺素
Keywords (in English): Rh(I)-Catalyzed, Conjugate Addition, Prostaglandin
DOI URL: https://doi.org/10.6345/NTNU202204537
Thesis Type: Academic thesis/ dissertation
Reference times: Clicks: 144Downloads: 0
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  • 本篇論文在探討 (1)利用一價銠金屬作為催化劑,以甲醇當溶劑,氫氧化鉀作為鹼性添加劑,在低溫條件下(3 °C),催化(R)-47與各種不同芳香基以及烯基硼酸的共軛加成反應,得到單一非鏡像異構物 52。此反應利用於他氟前列素 (tafluprost 3) 的合成。 (2)使用起始物(±)-68利用掌性雙環[2.2.1]配基L1與一價銠金屬形成之催化劑催化與烯基硼酸進行1,4-共軛加成反應,可以得到29−44%的產率以及90−98%的鏡像超越值。

    In this thesis, a conjugate reaction of a variety of aryl- and alkenyl- boronic acids, in the presence of 1.5 mol% of [RhCl(COD)]2 catalyst with (R)-47 is described. The conjugate addition reactions conducted at 3 °C, employing 1.2 equiv KOH as the basic additive and using MeOH as the solvent proceeded in a high diastereoselective fashion to give the conjugate adduct in 52−99% yield. In addition, the enantioselective conjugate addition reaction of 68 with 51a, catalyzed by 3 mol% of Rh(I)/L1 was also studied. Compound 79 was obtained as a single diastereomer in 90−98% ee.

    目錄 謝誌 中文摘要 英文摘要 英文縮寫對照表 第一章 緒論1 第二章 前列腺素合成之文獻回顧4 第三章 銠金屬催化之實驗設計與概念13 第四章 實驗結果與討論(一)18 第五章 立體化學之探討30 第六章 他氟前列素的合成31 第七章 實驗設計與概念32 第八章 實驗結果與討論(二)43 第九章 立體化學之鑑定46 第十章 結論49 第十一章 實驗部分50 第十二章 參考文獻84 1H及13C NMR 圖譜86

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