本篇論文主要研究，利用不同的金雞鈉鹼衍生的催化劑進行有機不對稱的催化反應來建構具有高鏡像選擇性的螺環產物。
第一部分，設計可在反應中同時扮演親核性試劑與親電子性試劑的香豆素衍生物31，與1,3-茚二酮烯類衍生物30進行協同反應 (concerted) 及逐步反應 (stepwise) 行 [3+2] 反應合環，建構單一非鏡像異構物、高鏡像選擇性且具有四個掌性中心的螺環骨架化合物，並利用各種控制實驗，觀察到逆反應的存在以及鏡像超越值的變化，藉此推導其可能的反應機構。
第二部分，以1,3-茚二酮烯類衍生物 30 與 ,-不飽合酮類 39 進行有機不對稱共價催化反應，建構具有高非鏡像與高鏡像選擇性的螺環骨架的環己酮衍生物 40，且其種一個在環己酮環上 位加成官能基的反式純鏡像螺環骨架衍生物可以差向異構形成熱力學穩定的順式產物，只有些微降低鏡像選擇性，藉此證明了本文所推導的反應機構。
反應機構會經由兩種互相競爭的反應路徑，一個是Diels−Alder反應，另一個是逐步的Michael加成，藉此形成所對應的產物。

In my thiesis, the cinchona alkaloid derived organocatalysts were utilized for the synthesis of cyclohexanone and cyclopentanone derivatives via the covalent or non-covalent asymmetric organocatalysis.

In the first part, a new class of coumarin derivatives, bearing an electrophilic and a nucleophilic site at the same time, have been developed. Cinchona alkaloid-derived chiral hydrogen bonding catalysts were utilized to carry out the [3+2] cyclization of these coumarin derivatives with 2-alkylidene indandiones. The corresponding spiro products bearing four stereocenters, including an all-carbon quaternary center, were obtained as single diastereomers with high enantioselectivity. The Michael addition intermediate was also isolated and a few control experiments have been performed to support the proposed mechanism.

In second part, a cinchona-alkaloid derived chiral primary-amine-catalyzed enantioselective spirocyclohexanones derivatives is demonstrated. Both the enantiomeric forms of the trans isomer are obtained in excellent yields and enantioselectivities. Mechanistic investigations revealed two competing pathways, a concerted Diels−Alder reaction and a stepwise Michael addition, for the formation of corresponding products.

簡 歷 II
摘要 III
ABSTRACT IV
謝誌 V
目錄 VII
第一章 以新開發的香豆素衍生物進行有機不對稱催化反應經 [3+2] 合環合成具有高鏡像選擇性的螺環化合物 1
1-1前言 1
1-1-1 香豆素介紹 1
1-1-2 香豆素於有機不對稱領域中常見的反應 2
1-2 研究動機 6
1-3實驗結果與討論 8
1-3-1 非掌性催化劑之最佳化 8
1-3-2 掌性催化劑之最佳化 10
1-3-3 溶劑之最佳化 12
1-3-4 催化劑使用量及添加劑之最佳化 14
1-3-5 反應溫度之最佳化 16
1-3-6 取代基變化的影響 17
1-3-6-1 R1 取代基的變化 17
1-3-7 大量化 20
1-3-8 反應機構的探討 21
1-4 結論 25
1-5 實驗部分 26
1-5-1 分析儀器及基本實驗操作 26
1-5-2 反應步驟 28
1-5-3 產物數據 29
1-6 參考文獻 43
第二章 擴展有機不對稱一級胺催化的適用範圍：合成具有高鏡像選擇性的1,3-茚二酮并2,6雙取代反式螺環環己酮 46
2-1 前言 46
2-1-1 有機不對稱共價催化 46
2-2 研究動機 52
2-3實驗結果與討論 54
2-3-1 催化劑的最佳化 54
2-3-2 溶劑的最佳化 56
2-3-3 催化劑與添加劑使用量最佳化 58
2-3-4 添加劑的最佳化 60
2-3-5 溫度與當量的最佳化 64
2-3-6 取代基的變化 66
2-3-6-1 R1 取代基變化 67
2-3-6-2 R2 取代基變化 68
2-3-6-3 嘗試不同親核試劑 72
2-4 具有C2旋轉軸的產物特性 75
2-5 三組分反應並進行大量化 76
2-5-1 三組分反應 76
2-5-2 大量化 77
2-6 反應機構 78
2-7 結論 83
2-8 實驗部分 84
2-8-1 分析儀器及基本實驗操作 84
2-8-2 反應步驟 86
2-8-3 產物數據 88
2-9 參考文獻 120
附錄一 122
附錄二 209
附錄三 255

第一部分

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