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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