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研究生： 黃俊傑
論文名稱： Synthetic studies on functionalized chiral cyclopentanones
指導教授： 磯部 稔
Minoru Isobe
口試委員: 汪炳鈞
吳學亮
磯部 稔
學位類別： 碩士
Master
系所名稱： 理學院 - 化學系
Department of Chemistry
論文出版年： 2013
畢業學年度： 101
語文別： 英文
論文頁數： 110
中文關鍵詞： 有機合成 、不對稱 、前列腺素E2
外文關鍵詞： Organic synthesis, Asymmetry, Prostaglandin E2
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    • 本論文中，我們將著重於運用異原子引導共軛加成與環化反應(HADCAC)來建構前列腺素E2的不對稱環戊酮骨架。其設計的合成路徑裡包含: (1)化合物107和96運用埃文斯羥醛不對稱反應來建構(R)立體結構的化合物(R)-109。 (2)運用改良的毛思迪方法確認化合物(R)-109中醇基的絕對組態。 (3)化合物(R)-109與鋰正辛炔進行異原子引導共軛加成與環化反應得到環戊酮(R)-112，但與烯基親核試劑卻無法建構環戊酮。(4) 為改善異原子引導共軛加成與環化反應，化合物(R)-109由取代反應獲得溫勒伯醯胺(R)-129。 (5)溫勒伯醯胺(R)-129與正辛烯鋅酸鋰鹽進行異原子引導共軛加成與環化反應可得到環戊酮(R)-127。

    In this thesis, we focused our attention on constructing the chiral cyclopentanone skeleton of PGE2 through heteroatom-directed conjugate addition and cyclization (HADCAC). The synthetic routes includes: (1) The (R)-configuration alcohol (R)-109 was established from Evans asymmetric aldol reaction by the boron enolate of (R)-oxazolidinone 107 and the vinylsulfone aldehyde 96. (2) The absolute configuration of the secondary alcohol (R)-109 was confirmed by the modified Mosher’s method. (3) The chiral cyclopentanone (R)-112 was obtained from HADCAC of oct-1-ynyllithium to the oxazolidinone (R)-109, but the result of the vinyl nucleophile was failed. (4) The Weinreb amide (R)-129 was implemented from the oxazolidinone (R)-109 for improvement of HADCAC. (5) The chiral cyclopentanone (R)-127 was obtained from the HADCAC of the vinyl zincate to the Weinreb amide (R)-129.

    中文摘要 Abstract Acknowledgements Contents Abbreviations Figure index Table index Scheme index Chapter 1 Introduction 1-1 Introduction of Prostaglandin E2 1-2 Total synthesis of Prostaglandin E2 1-3 Introduction of heteroatom-directed conjugate addition 1-4 Introduction of heteroatom-directed conjugate addition and cyclization Chapter 2 Results and Discussion 2-1 Asymmetric aldol reaction 2-2 Heteroatom-directed conjugate addition and cyclization 2-3 Modification of the oxazolidinone derivatives Chapter 3 Conclusion Chapter 4 Experimental 4-1 Experimental section 4-2 Reference Appendix

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