臺灣博碩士論文加值系統

壹、 摘要
本論文是在研究利用手性胺基酸為原料製備雙手性胺醇及雙手性胺基硫醇
作為不對稱催化反應的掌性催化劑 , 並與鎳錯化合物 ( Ni complexes )存在下 ,
催化二乙基鋅 ( diethylzinc ) 對查耳酮 ( 苯基苯乙基甲酮 , chalcone ) 進行不對
稱的 1,4 加成反應( 1,4-addition reaction ) , 結果顯示在 -30℃的反應溫度下 ,
可得到高達 92.5 % e.e的鏡像超越值( enantioselectivity ) 。
在掌性配基的探討方面 , 文獻上已有許多各種不同型式的胺基醇 , 但它
們皆是以氮原子及氧原子為主的雙牙基掌性配體( bidentate ligand ) 來做手性源
( chiral source ) 。 現在 , 我們更進一步將氧原子改成硫原子 、 作成硫醇 ( thiol )
及硫代乙酸酯 ( thioacetates ) , 另外我們也針對了掌性配基的取代基上的變化 、
反應的溶劑 、 反應的溫度 、 掌性配基的用量及不同的鎳錯化合物等因素進行
探討 , 以求得最佳的反應條件及更佳之鏡像催化效果 。 最後提出可能的反應
機構用以合理的解釋我們目前的實驗結果 , 期盼對日後雙手性胺基醇及胺基硫
醇類的催化劑開發能更有助益 。

Abstrate
The research in this thesis focuses on how using amino acid as a starting material, we produce chiral amino alcohol and chiral amino thiol to be a chiral catalyst. With the co-existence of Ni complexes, causing the catalysis of diethylzinc, we proceed 1,4-addition reaction on chalcone. The result show that under the condition of —30°C reaction temperature, we can get the enantioselectivity up to 92.5% e.e.
In the study of chiral ligand, we have seen all kinds of amino alcohol in many references, but all of them used N atom and O atom as the main part of bidentate to be the chiral source. Now moving further ahead, we change O atom into S atom to make thiols and thioacetates. On the other hand, we also study the factors that may influence the reaction, including the change of the substitution of chiral legand, the reaction solvent, the reaction temperature, the dose of chiral ligand and the different Ni complexes, in order to get the best reaction condition and the best effect of enatioselectivity. At last, we propose the possible mechanism to logically explain the result of our experiment, expecting that it can bring much more benefit to the future producing of chiral amino alcohol and amino thiol.

一. 摘要 1
二. 導論 2
三. 結果與討論 18
四. 結論 37
五. 儀器測定及物質處理 38
六. 實驗步驟 39
七. 參考資料 49
八. 光譜 51

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