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研究生：	陳怡惠 Chen, Yi-Hui
論文名稱：	藉由假絲酵母玫瑰脂脢對於1-苯基-1,3-丁二醇之四個立體異構物進行動力解析：具有高度的位向及立體選擇性之反應 Kinetic Resolution of Four Stereoisomers of 1-Phenylbutane-1,3-diol by Candida Rugosa Lipase: Highly Regio- and Stereoselectively reaction
指導教授：	宋光生 Sung, Kuangsen
學位類別：	碩士 Master
系所名稱：	理學院 - 化學系 Department of Chemistry
論文出版年：	2006
畢業學年度：	94
語文別：	中文
論文頁數：	57
中文關鍵詞：	酵素、動力解析
外文關鍵詞：	enzyme, kinetic resolution
相關次數：	點閱：121 下載：1
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　　脂脢為普遍使用的酵素之一，其可以催化不對稱合成，得到高純度的不對稱化合物。脂脢對於受質具有寬的特異性及高度的立體選擇性，使得它有效地被有機化學家所使用。在此，我使用脂脢之一的假絲酵母玫瑰脂脢，進行1-苯基-1,3-丁二醇(1)高度地位向及立體選擇性的轉酯化反應。對於(±)-syn-1使用假絲酵母玫瑰脂脢的動力解析，得到高度立體選擇性的(+)-syn-2及(-)-syn-3 (式1)；相對於(±)-anti-1的動力解析，則得到高度立體選擇性的(+)-anti-3及(-)-anti-1 (式2)。syn-2發生分子內之轉酯化反應較syn-3快，故(-)-syn-3得到較低的ee值。然而，在anti-3之反應當中沒有發生分子內的轉酯化反應。

　　Lipases, which are one of the most commonly used enzymes, catalyzed asymmetric synthesis to afford high purely chiral compounds. Their broad substrate specificity and high stereoselectivity make them useful to the organic chemist. Herein I report highly regio- and stereoselective transesterification of 1-phenylbutane-1,3-diol (1) by Candida rugosa lipase (CRL) which is one of the most useful lipases. Kinetic resolution of (±)-syn-1 by CRL generated (+)-syn-2 and (-)-syn-3 highly stereoselectively, whereas kinetic resolution of (±)-anti-1 by CRL produced (+)-anti-3 and (-)-anti-1 highly stereoselectively. Intramolecular transesterification occurred in syn-2 faster than that in syn-3, resulting in less e.e. value of (-)-syn-3. However, there is no intramolecular transesterification found in anti-3.

中文摘要----------------------------------------------------------------------1
英文摘要----------------------------------------------------------------------2

第一章 緒論------------------------------------------------------------------11
1-1純的鏡像立體異構物之合成路徑的簡介----------------------------------------11
    1-1-1 路徑一-------------------------------------------------------------11
    1-1-2 路徑二-------------------------------------------------------------11
    1-1-3 路徑三-------------------------------------------------------------13
1-2 受質簡介-----------------------------------------------------------------14
    1-2-1  1-苯基-1,3-丁二醇的結構-------------------------------------------14
    1-2-2  不對稱1,3-二醇立體選擇性之過去合成方法----------------------------15
    1-2-3  不對稱1,3-二醇立體選擇性之酵素催化合成方法------------------------16
    1-2-4  不對稱1,3-二醇的效用----------------------------------------------18
1-3 酵素的簡介---------------------------------------------------------------19
    1-3-1 酵素的特性---------------------------------------------------------19
    1-3-2 酵素的種類---------------------------------------------------------19
    1-3-2A 水解脢的簡介------------------------------------------------------20
    1-3-2B 水解脢的特徵------------------------------------------------------21
    1-3-2C 水解脢的種類------------------------------------------------------22
    1-3-2D 醯化反應的醯類供給者(acyl donor)之簡介----------------------------24
    1-3-2E  簡介Kazlauskas rule----------------------------------------------26
    1-3-2F  CRL催化反應的機制------------------------------------------------26
    1-3-2G  鏡像異構物的過量及鏡像異構物的比率之探討-------------------------28

第二章 實驗結果與討論--------------------------------------------------------30
2-1 合成受質1-苯基-1,3-丁二醇------------------------------------------------30
2-2 (±)-syn-1-苯基-1,3-丁二醇(1)之動力解析-----------------------------------31
2-3 (±)-anti-1-苯基-1,3-丁二醇(1)之動力解析----------------------------------39
2-4 總結---------------------------------------------------------------------42

第三章 實驗步驟--------------------------------------------------------------43
	Preparation of (±)-4-hydroxy-4-phenylbutan-2-one (6)----------------43
	Preparation of (±)-l-Phenylbutane-1, 3-diol (1)---------------------44
	Enzymatic resolution of 1, 3-diol (1)-------------------------------44
	Protected reaction with phenyl isocyanate---------------------------45
	Oxidation with PCC (pyridine chlorochromate)------------------------46
	Preparation of racemate of (±)-3-oxo-1-phenylbutyl acetate (4)------47
	Preparation of racemate of (±)-4-oxo-4-phenylbutan-2-yl acetate (5)-48

第四章 數據分析--------------------------------------------------------------50
	(±)-4-hydroxy-4-phenylbutan-2-one (6)-------------------------------50
	(±)-syn-l-Phenylbutane-1, 3-diol (1)--------------------------------50
	(±)-anti-l-Phenylbutane-1, 3-diol (1)-------------------------------50
	(±)-syn-3-hydroxy-1-phenylbutyl acetate (2)-------------------------50
	(±)-syn-4-hydroxy-4-phenylbutan-2-yl acetate (3)--------------------51
	Chiral HPLC analysis of (+)-syn-1-----------------------------------51
	(±)-anti-4-hydroxy-4-phenylbutan-2-yl acetate (3)-------------------51
	(±)-3-oxo-1-phenylbutyl acetate (4)---------------------------------52
	(±)-4-oxo-4-phenylbutan-2-yl acetate (5)----------------------------52
	Chiral HPLC analysis of (+)-4---------------------------------------52

第五章 參考資料--------------------------------------------------------------53
第六章 未來計畫--------------------------------------------------------------55

                                    

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校內：2007-06-22公開
校外：2007-06-22公開

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