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研究生:鍾佑強
研究生(外文):CHUNG YU-CHIANG
論文名稱:高鏡像選擇性銠(I)/掌性雙烯配體催化芳香基硼酸對反丁烯二酸酯進行不對稱1,4加成反應及其合成應用 -α2腎上腺素受體拮抗劑全合成 -氮-苄基-3-苯基吡咯啶的不對稱合成
指導教授:吳學亮
指導教授(外文):Hsyueh-Liang Wu
學位類別:碩士
校院名稱:國立臺灣師範大學
系所名稱:化學系
學門:自然科學學門
學類:化學學類
論文種類:學術論文
論文出版年:2011
畢業學年度:99
語文別:中文
論文頁數:247
中文關鍵詞:反丁烯二酸酯不對稱14-加成
外文關鍵詞:rhodiumfumarateasymmetric 1,4-addition
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  利用天然物左旋醋酸冰片酯49合成高穩定性的掌性雙環[2.2.1]雙烯配體,並結合銠(I)催化芳香基硼酸對反丁烯二酸酯進行不對稱1,4-加成反應。在這個催化系統中,銠(I) (1mol% of Rh)催化量和掌性雙烯配體進行不對稱1,4-加成反應,產物具有高產率和高立體選擇性(高達>99.5% ee值)。並將其應用在合成掌性3-(2-甲氧基)苯基吡咯啶(α2 -腎上腺素受體拮抗劑)和合成掌性氮-苄基-3-苯基吡咯啶。
A new set of stable chiral bicyclo[2.2.1] diene ligands were prepared from (-)-bornyl acetate 49, and were employed in the rhodium(I)-catalyzed asymmetric 1,4-addition of arylboronic acids to fumarates. In this catalytic system, rhodium-diene complex (1.0 mol%) generated in situ from chiral diene 53a and [RhCl(C2H4)2]2 successfully yielded the corresponding adducts with good to excellent chemical yields and excellent levels of enantioselectivities (up to >99.5% ee). This methodology was demonstrated by its utilization in the enantioselective total synthesis of 3-(2-methoxyphenyl)pyrrolidine (an α2-adrenoceptor antagonist) and asymmetric synthesis of N-benzyl-3-phenylpyrrolidine.
第一章 緒論..................... 1
第二章 文獻回顧................... 6
第三章 設計理念.................. . 15
第四章 實驗結果與討論................ 19
4-1 製備掌性[2.2.1]雙烯配體.............. 19
4-2 銠(I)金屬結合掌性配體催化不對稱 1,4-加成在 Fumaric 化合
物.......................... 20
4-2-1 改變加料順序及配位時間.............. 21
4-2-2、調整銠(I)催化量................. 23
4-2-3、改變配體上的芳香族官能基............ 24
4-2-4、溶劑效應................... 26
4-2-5、鹼效應..................... 28
4-2-6、最好條件下調整銠(I)催化量............ 29
4-2-7、底物例子(Substrate Scope) ............ 29
4-2-8、X-ray 繞射結構圖及預測立體化學路徑...... 32
第五章 合成與應用............... 36
5-1、前言.................... 36
5-2 文獻回顧................... 36
5-3、合成與應用................... 39
第六章 實驗步驟................. . 43
參考文獻....................... 93
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