一、對掌乙醛醯胺之不對稱親核性加成反應。二、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。

潘佳甫(Jia-fu Pan)

指導教授 ： 陳焜銘

國立臺灣師範大學/理學院/化學系/博士(2003年)

摘要

無資料

關鍵字

樟腦 ； 乙醛醯胺

並列摘要

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%).

並列關鍵字

camphor ； glyoxylate

參考文獻

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