研究生: |
林旺俊 |
---|---|
論文名稱: |
具C-3或C-5芳香基取代之N-亞柳胺基酸衍生之掌性氧釩錯合物催化不對稱有氧性氧化及布對稱1,4-加成反應之研究 Chiral C-3 or C-5 Substituted N-Salicylidene Vanadyl Carboxylate Catalyzed Enantioselective Aerobic Oxidation and Enantioselective 1,4-Addition |
指導教授: | 陳建添 |
學位類別: |
碩士 Master |
系所名稱: |
化學系 Department of Chemistry |
論文出版年: | 2009 |
畢業學年度: | 97 |
語文別: | 中文 |
論文頁數: | 83 |
中文關鍵詞: | 氧釩錯合物 、催化 、有氧性氧化 、1,4-加成 |
英文關鍵詞: | oxovanadium complex, catalyszed, aerobic oxidation, 1,4-addition |
論文種類: | 學術論文 |
相關次數: | 點閱:122 下載:0 |
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我們延續實驗室既有之系統,合成N-亞柳胺基酸衍生之掌性希夫鹼與氧釩金屬所形成之錯合物並將其應用於催化有氧性不對稱氧化以及不對稱1,4-加成反應上。為了增加芳香環之立障,我們設計了2,5-二甲基苯與2,4,5-三甲基苯兩種芳香環取代基,並同時接在錯合物的C-3以及C-5位置上合成雙芳香環錯合物5、6;另外,我們也嘗試在C-5位置上引入擁有強拉電子性質的硝基合成錯合物7、8、9。
3,5-雙溴取代之錯合物在過去的研究中對於芳香環取代的苯基α-羥基亞磷酸二苄酯進行有氧性不對稱氧化的催化效果非常好,但在非芳香環取代的苄基 α-羥基亞磷酸二苄酯的實驗中,我們發現3-溴-5-硝基取代之錯合物7效果卻更加優異。
而於對α-羥基酮類進行之有氧性不對稱氧化的實驗中,我們發現C-5位置上接上具強拉電子性質的硝基取代之錯合物,對於此類反應之催化效果都不錯,其選擇性因子最高可達35。
在1,4-加成反應方面,對於2-酮基環戊基甲酸苄酯進行催化時,鏡像超越值可達51%,而對於1-酮基-2-苯駢環丙烷甲酸苄酯及其衍生物,鏡像超越值可達74%。
A series of chiral vanadyl(V) methoxides bearing 3,5-diaryl substituted or 3-aryl-5-nitro substituted N-salicylene-L-t-leucinate as chiral auxiliaries has been prepared.
In comparison with the 3,5-dibromo substituted vanadyl(V) methoxide complex, the 3-bromo-5-nitro substituted vanadyl(V) methoxide complex 7 was utilized to facilitate the asymmetric aerobic oxidations of dibenzyl (hydroxy-benzyl-methyl)-phosphonate with better selectivity factor. And the C-5 nitro substituted complexes serve as highly enantioselective catalysts for asymmetric aerobic oxidation of α-hydroxy-ketones at ambient temperature with selectivity factor ranging from 12 to 35.
When applied in the 1,4-addition of benzyl 2-oxocyclopentane- carboxylate and benzyl 1-oxo-2-indanecarboxylate with MVK, these complexes promoted the reaction in 93-99% yield, 22-74% ee at room temperature.
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