研究生: |
彭俊翰 Peng chun-han |
---|---|
論文名稱: |
非鏡像選擇性之環丙完化反應探討 Diastereoselective Cyclopropanation Reaction |
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: | 2004 |
畢業學年度: | 92 |
語文別: | 中文 |
論文頁數: | 210 |
中文關鍵詞: | 樟腦 、對掌環丙烷 、非鏡像選擇性 、對掌試劑 、對掌輔助劑 |
英文關鍵詞: | camphor, chiral cyclopropane, diastereoselective, chiral reagent, sulfonium ylides, chiral michael aceptor, chiral auxiliary, MIRC |
論文種類: | 學術論文 |
相關次數: | 點閱:222 下載:8 |
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用本實驗開發之對掌輔助劑(78、79),製備對掌α,β-不飽和烯類與對掌sulfonium ylides,進行不對稱MIRC(Michael Initiated Ring Closure)反應,分別從兩個面向對環丙烷進行不對稱合成探討。
使用對掌輔助劑 79衍生之α,β-不飽和酯基,以 sulfonium ylides(85)作為親核性試劑,針對不同取代基進行反應,可以獲得好的產率(73-96%),特別是使用無取代的酯基作為基質時,可以在短時間內(2h)得到高非鏡像選擇性(>90% de);使用對掌輔助劑 78衍生之α,β-不飽和烯類,以sulfonium ylides作為親核性試劑,可以獲得良好的產率(43-94% yield)。尤其當α或是β位置有取代基時,可以得到單一的光學異購物(>90% de)。
以對掌輔助劑 78衍生之對掌sulfonium ylides(107),利用二甲亞碸做為溶劑,在室溫下與α,β-不飽和酯基、醯胺、酮基、氰基進行反應,順利得到環丙烷分子(63-90%),對無取代與α取代基的烯類有高非鏡像選擇性(76-90% de),主要產物之絕對組態經由X-ray單晶繞射分析確認為(1R, 2R)。經由推測之反應機構知道,由於環丙烷上的兩個羰基,受到立障影響以及偶極-偶極矩效應,產物偏好反式的構形。
環丙烷在有機合成上是重要的結構單體,本研究提供另一項對掌環丙烷合物之製備方法,以期應用於不對稱有機合成上。
Cyclopropane is an important building block found in many nature products. The preparation of enantiomerical pure compounds is one of the major areas in organic chemistry. The synthesis of cyclopropane and their derivaties has attracted a lot of attention in recent years, owing to their versatile roles in organic synthesis.
Cyclopropanation of chiralαβ-unsaturated olefins derived from a exo-10,10-diphenyl-2,10-camphanediol 79. We find that substrates are eletrophile olefins by using sulfonium ylides as ncleophile in good chemical yield (63-96% yield). Especially, cyclopropanation of chiral auxiliary 79 derives O-acrylate Ⅱ-15 gives high diastereoselectivity(>90% de). Cyclopropanation of chiralαβ-unsaturated olefins derived from a camphor pyrazolidinone 78.Only one optical isomer(>90% de) was obtained when using α- or β- substituted chiral olefins as substrates.
Cyclopropanation of chiral sulfonium ylides(107) derived from a camphor pyrazolidinone 78. We find that chiral reagents react with variousα,β-unsaturated olefins in moderate to good yield(63-90% yield).Good diastereoselectivity(76-90% de) was obtained when using non- or α-substituted unsaturated olefins as substrates.The absolute stereochemistry of the newly generated cyclopropane ring was determined to be a (1R, 2R)-configuration by single crystal X-ray analysis. The diastereoselectivity was determined by 1H-NMR analysis of the crude products.
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