| 研究生: |
陳福琳 Chen, Fu-Lin |
|---|---|
| 論文名稱: |
多組成反應之應用:高立體選擇性不對稱鹼
Eschweiler-Clarke methylation的例外研究:
利用甲醛、甲酸環化α-amino amide The Application of MCRs(Multicomponent Reaction):High diastereoselective chiral base A Exception of Eschweiler-Clarke methylation:Cyclocondensation of α-amino amide with Formaldehyde and Formic acid |
| 指導教授: |
宋光生
Sung, Kuang-Sen |
| 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: | 2004 |
| 畢業學年度: | 92 |
| 語文別: | 中文 |
| 論文頁數: | 90 |
| 中文關鍵詞: | 甲基化 、多組成反應 、不對稱鹼 |
| 外文關鍵詞: | MCRs, isocyanide, chiral base, Eschweiler-Clarke methylation |
| 相關次數: | 點閱:131 下載:1 |
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我們可經由高選擇性的3CR反應來製備α,α'-iminodiacetic acid的對掌異構物,它的合成方法是將異腈、醛類和純的L-或D-胺基酸在甲醇當溶劑下反應。所得到的對掌異構物的絕對組態,是由合成過程中的胺基酸所決定。L-胺基酸產生一對掌異構物,那麼D-胺基酸所生成的必是另一個對掌異構物. 而且此3CR反應對於醛類、胺基酸的取代基大小相當的敏感。
在α-amino amides上,我們找到了Eschweiler-Clarke methylation反應的另一項發現。正常的Eschweiler-Clarke methylation是將氮上接上一個甲基,所使用的試劑是甲酸跟甲醛,但是在α-amino amides我們得到的卻是環化的產物,但是並非所有的α-amino amides對於甲酸甲醛的反應皆是得到環化產物,當結構上取代基的立體障礙過大的時候,還是會得到甲基化的產物的。
Several pairs of enantiomeric α,α'-iminodiacetic acid analogues were prepared separately by highly diastereoselective 3CR,which involves a reaction of an isocyanide, an aldehyde, and an enantiomerically pure amino acid in methanol. Synthesis of each of the enantiomers was controlled by the configuration of the amino acid;L-amino acid produces one enantiomer and D-amino acid generates the other. The diastereoselectivity of the 3CR is very sensitive to the substituent size of both aldehyde and enantiomerically pure amino acid.
An exception of Eschweiler-Clarke methylation was found for α-amino amides. Theα-amino amides on treatment with formaldehyde and formic acid produce cyclocondensation products, imidazolidin-4-ones, while N-methylation process becomes important when three substituents of theα-amino amides are very bulky. However, N-methylation is the only product for Eschweiler-Clarke methylation of the α-amino amides with N,N-disubstituted amides
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