夲論文主要分為兩個部分：第一部分為探討對掌乙醛醯胺之不對稱親核性加成反應。樟腦衍生之對掌乙醛醯胺19已被成功的製備出來。對掌輔助劑14與乙二醯氯在二氯甲烷下反應，得到單一醯化產物，以Bu3SnH當還原劑，在苯當溶劑下反應，可得到84%的產率，經1H-NMR、13C-NMR、HRMS作分子結構的鑑定，判定產物無誤。以對掌乙醛醯胺當作親電子試劑進行貝里斯-希爾曼反應，在三級胺DABCO的催化下，以DMSO/H2O為溶劑下反應，得到2-hydroxy-3-methylene 琥珀酸的衍生物，有極高的非鏡像選擇性(>90% de)和中等的產率(51-75%)。以對掌乙醛醯胺當作親電子試劑進行Carbonyl-Ene反應，在路易士酸Sc(OTf)3的催化下，以二氯甲烷為溶劑下反應，得到2-hydroxy-4-methylene 的衍生物，有不錯的非鏡像選擇性(73-94% de)和中等的產率(61-87%)。
第二部分為新型對掌螯合劑之設計合成及探討其在有機不對稱合成上的應用。以樟腦酮菘酸117為合成新型對掌螯合劑的主要架構。利用各種不同的雙胺分子與樟腦酮菘酸進行反應，成功的得到具有C2對稱的對掌螯合劑。分子結構經由1H-NMR光譜或X-ray單晶繞射確認。樟腦衍生之對掌螯合劑128與醋酸錳錯合，可以選擇性氧化苯甲基的碳氫鍵，並且得到高產率的產物。在5 mol%的錯合物催化下，以2.0當量第三丁基過氧化氫當氧化劑，在二氯甲烷的溶劑下，只需要反應5-30分鐘。.以樟腦所衍生之對掌螯合劑催化chalcone的不對稱環氧化反應。在篩選各種樟腦衍生的對掌螯合劑與路易士酸後，反應結果並不理想，鏡像選擇性最高只有14%，產率40%。樟腦衍生之對掌螯合劑128與醋酸錳錯合，搭配m-CPBA的氧化劑，對trans-stilbene進行環氧化反應，可以得到84%的鏡像選擇性，產率小於20%。以樟腦衍生之對掌螯合劑催化2-萘酚202的不對稱偶合反應。以對掌螯合劑67搭配氯化銅來催化2-萘酚的氧化偶合反應，可以得到55 % ee的鏡像選擇性，產率49%。

Ⅰ. Stereoselective Addition of Nucleophiles to N-Glyoxyloyl Camphorpyrzolidinone
Treatment of camphorpyrazolidinone with oxalyl chloride (10 equiv) in CH2Cl2 gave the monoacylated product, which was reduced with Bu3SnH (1equiv) in benzene at room temperature for 10 min, offording N-glyoxylate camphorpyrazolidinone in 84% overall yield.The camphorpyrazolidinone derived N-glyoxylate was efficiently prepared and used as an electrophile in the Baylis-Hillman reaction under classical DABCO catalyzed condition. The corresponding 2-hydroxy-3-methylene succinic acid derivative was generally obtained with excellent diastereoselectivity and moderate chemical yield (51-75%).The camphorpyrazolidinone derived N-glyoxylate was used as an electrophile in the Carbonyl-Ene reaction under lewis acid Sc(OTf)3 catalyzed condition. The corresponding 2-hydroxy-4-methylene derivative was generally obtained with moderate to good diastereoselectivity (73-94% de) and moderate chemical yield (61-87%).
Ⅱ. Synthesis of Camphor-Derived Chiral Ligands and Their Synthetic Applications in Organic Reactions
Ketopinic acid was used as the chiral core structure in new camphor-derived chiral ligands synthesis. Different diamines were introduced to react with ketopinic acid and we had successfully obtained dimeric ligands. All chemical structures of dimeric ligands were further comfirmed with NMR study and X-ray single crystal analyses.Selective oxidation of activated hydrocarbons to the corresponding carbonyl functionality was achieved with good to high material yields using novel campor-derived ligands mediated with Mn(Ⅱ) as catalyst. In general, the reaction proceeds smoothly with 5mol% of catalyst and 2.0 equiv of t-BuOOH as oxidant in CH2Cl2 in 5-30 min.The camphor-derived chiral ligands was used in the epoxidation of Chalcone derived. We surveyed various camphor-derived chiral ligands and oxidants, but we only obtained with low enantiommeric selectiveties (14%) and moderate yield (40%). The epoxidation of trans-stilbene was achieved with low yield (<20%) and high enantiommeric selectiveties (84%) using novel campor-derived ligands mediated with Mn(Ⅱ) as catalyst and m-CPBA as oxidant.The camphor-derived chiral ligands was used in the enantioselective oxidative biaryl coupling of substituted 2-naphthol derivatives., the best results were obtained with moderate enantiommeric selectiveties (52%) and moderate yield (49%).

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