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| 研究生： |
吳正洋 |
|---|---|
| 論文名稱： |
壹、以樟腦架構為主的新穎對掌螯合劑之設計與合成 貳、α,β-不飽和烯類與N-aminophthalimide之 |
| 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： | 192 |
| 中文關鍵詞： | 樟腦 、對掌螯合劑 、氮丙啶 、不飽和烯類 |
| 英文關鍵詞： | chiral ligand, aziridination, camphor, α,β-unsaturated olefin |
| 論文種類： | 學術論文 |
| 相關次數： | 點閱：166 下載：0 |
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摘要
I
樟腦菘酮酸65為新穎對掌螯合劑之核心結構。藉由樟腦菘酮酸醯氯與具有不同的非掌性平面模版的胺類或醇類作用，分別得到產率不錯的camphyl-10-amides 67-70與camphyl-10-ester 66，此酮類衍生物為製備對掌螯合劑的前驅物。將化合物67與70在室溫下，以甲醇為溶劑與NaBH4 進行還原反應，可以得到相對應的2-exo-hydroxy camphyl-10-amides 71與72，所有化合物的分子結構由NMR圖譜或X光單晶繞射來確認。
II
我們製備具有不同平面模版的α,β-不飽和烯類82-89與N-aminophthalimide進行鏡像氮丙啶化反應。許多由本實驗室所製備的對掌螯合劑被篩選，僅具有雙羧酸根結構的對掌螯合劑100展現良好的鏡像選擇性。在不同的平面模版中，由oxazolidinone-α,β-不飽和烯類 89a與對掌螯合劑100的組合可以得到最佳的鏡像選擇性。藉由具有不同取代基的oxazolidinone α,β-不飽和烯類 89a-f為起始物，加入N-aminophthalimide，以二氯甲烷為溶液，在0 ℃下，與對掌螯合劑100錯合的四價醋酸鉛複合物反應，可快速地得到高產率的鏡像氮丙啶101a-f （83-99%），鏡像選擇性63-95% ee。鏡像氮丙啶101a-f的絕對立體組態藉由與對掌輔助劑111的置換後結晶的X光單晶繞射確認。在此反應中，對掌螯合劑的結構對於鏡像選擇性有很大影響，需為二聚體結構且具有羧酸根。α,β-不飽和烯類上平面模版對鏡像選擇性也有極大的影響，α,β-不飽和烯類必須有1,3-雙羰基的結構才能獲得最佳的選擇性。溶劑效應與可能的反應機構也被探討。
Abstract
I
Ketopinic acid 65 is used as the chiral core structure in our new camphor-based ligand design and synthesis. Different achiral templates are introduced to react with ketopinoic chloride and we had successfully obtained camphyl-10-amides 67-70 and camphyl-10-ester 66 in good yield as precursors for further synthesis of novel ligands. On treatment of ketopinic amide 67 and 70 with NaBH4 as reductant in MeOH obtained 2-exo-hydroxy-camphyl-10-amides 71 and 72, which can be used for further study. All chemical structures of ketopinic amide and ester derivatives are further comfirmed with NMR study and X-ray single crystal analyses.
II
α,β-Unsaturated olefins 82-89 are prepared to participate enantiomeric aziridination with N-aminophthalimide as nitrene source. We had surveyed various ligands but only dimeric ligand possessing carboxylic acid functionality 100 showed good enantiomeric selectivity. Among different achiral templates, we have obtained the highest enantiomeric selectivity with oxazolidinone a,b-unsaturated olefin 89a, hence we tried different substituted oxazolidinone a,b-unsaturated olefin 89a-f as starting materials. The reaction was carried on in CH2Cl2 in 0 oC mediated by lead(IV) tetracetate chelated with dimeric ligand 100. The corresponding aziridines 101a-f were obtained in high yields (80-95%) and with moderate to good enantiomeric selectivities (63-95% ee). The absolute configurations of aziridines were confirmed by attachment of camphor pyrazolidinone 13 to the previously prepared chiral aziridine. Achiral template effect and solvent effect are examined. The enantiomeric selectivity induced by ligand structures was observed and the possible mechanism was proposed.
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