研究生: |
陳鵬旭 |
---|---|
論文名稱: |
壹、設計並合成以樟腦為基本架構之對掌輔助劑;貳、對掌α,β-不飽和醯胺與苯乙基胺之非鏡像氮丙啶合成反應 |
指導教授: |
陳焜銘
Chen, Kwun-Min |
學位類別: |
碩士 Master |
系所名稱: |
化學系 Department of Chemistry |
論文出版年: | 2002 |
畢業學年度: | 90 |
語文別: | 中文 |
論文頁數: | 95 |
中文關鍵詞: | 樟腦 、對掌 、氮丙啶 |
英文關鍵詞: | camphor, chiral, aziridine |
論文種類: | 學術論文 |
相關次數: | 點閱:172 下載:0 |
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本論文探討以對掌輔助劑控制立體化學中心的建立,利用以樟腦架構為主的對掌輔助劑衍生之對掌醯胺,進行非鏡像的氮丙啶合成反應,生成具有非鏡像選擇性的氮丙啶。對掌輔助劑的製備以 (S)-樟腦酮菘酸 (ketopinic acid) 為起始物,經三步合成步驟所得,總產率在 74% 以上,對掌輔助劑的分子結構由 1H 與 13C NMR 圖譜鑑定,其絕對立體化學結構由 X-ray 單晶繞射解析確定。所衍生的α,β-不飽和醯胺先以過溴化溴口比啶及三乙基胺進行溴化取代,再與苯乙基胺反應,得到所需之氮丙啶的非鏡像超越值達 60% de,產物之立體化學結構由 X-ray 單晶繞射確定。
Camphor-derived chiral auxiliary camphor pyrazolidinone were prepared and used for asymmetric aziridination. Camphor pyrazolidinone was prepared from the known (S)-ketopinic acid in 3 steps in a total of 74% yield. The structure and absolute stereochemistry of the chiral auxiliary was assigned unambiguously by 1H, 13C NMR spectrum and X-ray crystallographic analysis. The derived N-enoyl pyrazolidinone was reacted with pyridinium hydrobromide perbromide and triethyl amine, then reacted with benzyl amine to obtain desired aziridine in 60% de.
1.Varinder K. Aggarwal*, Alison Thompson, Ray V. H. Jones, and Mike C. H. Standen, J. Org. Chem. 1996, 61, 8368-8369
2.Kung-Shuo Yang and Kwunmin Chen*, Org. Lett. 2000, 2, 729-731
3.Kung-Shuo Yang and Kwunmin Chen*, J. Org. Chem. 2001, 66, 1676-1679
4.Jon C. Antilla and William D. Wulff*, J. Am. Chem. Soc. 1999, 121, 5099-5100
5.Varinder K. Aggarwal*, and Marco Ferrara, Org. Lett. 2000, 2, 4107-4110
6.Michael P. Doyle*, Wenhao Hu, and Daren J. Timmons, Org. Lett. 2001, 3, 933-935
7.Jae Uk Jeong, Beata Tao, Ingo Sagasser, Hans Henniges, and K. Barry Sharpless*, J. Am. Chem. Soc. 1998, 120, 6844-6845
8.Alexander V. Gontcharov, Hong Liu, and K. Barry Sharpless*, Org. Lett. 1999, 1, 783-786
9.Sayyed Iliyas Ali, Milind D. Nikalje, and A. Sudalai*, Org. Lett. 1999, 1, 705-707
10.Bhanu M. Chanda*, Renu Vyas, and Ashutosh V. Bedekar*, J. Org. Chem. 2001, 66, 30-34
11.Jason A. Halfen*, Jason K. Hallman, John A. Schultz, and Joseph P. Emerson, Organometallics 1999, 18, 5435-5437
12.David B. Llewellyn, Dan Adamson, and Bruce A. Arndtsen*, Org. Lett. 2000, 2, 4165-4168
13.Tung Siu and Andrei K. Yudin*, J. Am. Chem. Soc. 2002, 124, 530
14.Andrew B. McLaren and J. B. Sweeney*, Org. Lett. 1999, 1, 1339-1341