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研究生： 朱常瑩
Chu Chang-Ying
論文名稱： 掌性釩錯合物在催化碳碳鍵生成反應之研究
Chiral Vanadium Complex Catalyzed the C-C Bond Formation Reaction
指導教授： 汪炳鈞
Uang Biing-Jiun
口試委員:
學位類別： 博士
Doctor
系所名稱： 理學院 - 化學系
Department of Chemistry
論文出版年： 2004
畢業學年度： 93
語文別： 中文
論文頁數： 181
中文關鍵詞： 掌性釩錯合物 、偶合反應 、不對稱 、腈醇反應 、腈胺反應
外文關鍵詞： Chiral vanadium complex, Coupling Reaction, Asymmetric, cyanohydrin, strecker reaction
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    • 本論文由胺基酸及水楊醛合成一系列掌性釩錯合物，並試著將掌性錯合物應用於不對稱2-萘酚的偶合反應、不對稱腈醇的合成，以及不對稱腈胺的合成。
    在不對稱2-萘酚偶合反應中，以錯合物13為催化劑需加入三甲基矽氯加速反應進行；然而以錯合物19b為催化劑，則不需要添加劑即可催化產生BINOL產物，其鏡像選擇性可達75%。此外，利用釩錯合物31為催化劑以丙酮為溶劑則可催化生成腈醇產物，其鏡像選擇性介於72-90%。試著應用錯合物31於腈胺的不對稱生成反應，雖然反應性不差但誘導出的鏡像選擇性並不理想，以20 mol%的錯合物31催化下僅誘導出34% ee的腈胺產物。

    A series of chiral vanadium complexes were prepared with amino acid and salicylaldehyde. These chiral complexes have been utilized in the studies of asymmetric coupling of 2-naphthols, chiral cyanohydrins and chiral aminonitriles syntheses.
    In asymmetric coupling of 2-naphthols, addition of trimethylsilyl chloride was necessary to promote the reaction rate when complex 13 was the catalyst. However, when using complex 19b as the catalyst to catalyze the enantioselective coupling of 2-naphthols, the BINOL products were obtained with up to 75% ee without additive. For the cyanohydrins syntheses, the complex 31 was able to catalyze trimethylsilyl cyanation of aldehyde in acetone. The chiral cyanohydrins were obtained in high yield with 72-90% ee. This catalyst was further studied in aminonitriles formation, but the enantioselectivity was not satisfactory. In the presence of 20 mol% complex 31, the chiral aminonitrile was synthesized in 34% ee.

    中文摘要..................................................i 英文摘要..................................................ii 謝誌.....................................................iii 目錄.....................................................v 圖目錄...................................................vii 第一章 緒論...............................................1 第二章 掌性釩錯合物催化2-萘酚不對稱偶合反應...............8 2.1 前言..............................................8 2.1.1 具掌性聯苯化合物在不對稱反應上的應用.............9 2.1.2 具掌性聯苯類化合物的製備........................12 2.2.1 聯萘類化合物應用在不對稱催化反應................15 2.2.2合成BINOL及其衍生物的文獻回顧..................17 2.3 結果與討論.......................................26 2.4 結論.............................................55 第三章 掌性釩錯合物催化不對稱腈醇的合成..................56 3.1 前言.............................................56 3.2 文獻回顧.........................................58 3.3 結果與討論.......................................69 3.4 結論.............................................79 第四章 不對稱腈胺的合成..................................80 4.1 前言.............................................80 4.2研究動機..........................................90 4.3 結果與討論.......................................91 第五章 實驗部份..........................................97 5.1 一般實驗方法.....................................97 5.2 掌性釩錯合物製備方法.............................99 5.3 不稱偶合反應....................................106 5.4 不對稱腈醇的合成.................................111 5.5 不對稱腈胺的合成................................127 參考文獻................................................129 附錄一..................................................136 附錄二..................................................157

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