臺灣博碩士論文加值系統

本論文主要是以氮,氮-雙[3’, 5’-二特丁基亞柳基]-1,2-環己二胺 10與VO(acac)2所形成掌性錯合物18，應用於環氧丙烷與三甲基矽苯硫醚的不對稱開環反應的催化系統。以化合物18為不對稱開環反應的催化劑其優點為：一. 室溫下容易保存且穩定。二. 製備容易。以氮,氮-雙[亞柳基]-1,2-環己二胺 與VO(acac)2溶於乙醇加熱迴流後，即可得到高產率的釩金屬錯合物。經由本論文的研究，發現此催化反應的鏡像選擇性受到掌性配位基、溶劑、路易士酸、受質等因素影響而異﹔此反應的最佳條件為：使用0.05當量的掌性釩錯合物18，以乙醚作溶劑，在-30oC的溫度下，以三甲基矽苯硫醚即可有效催化不對稱開環反應，產生具73% ee的2-硫苯基環己醇。

Asymmetric syntheses of β-hydroxylsulfides are carried out by using chiral VO(salen) 18 complex at low temperature. The complex 18 is prepared from 3,5-di-tert-butyl-2-hydroxybenzaldehyde with optically pure (R,R)-cyclohexanediamine followed by reflux with VO(acac)2 in two steps. Complex 18 is stable at room temperature and easy to prepare.
In our research, the enantioselectivity of products are carried out by charging chiral ligand, solvent, lewis acid, substrate and maintaining at different temperatures (-30oC-rt). The active catalyst is prepared from 5 mol% of 18 in ether at —30oC, obtained 2-(phenylthio)cyclohexanol in 73% ee.

中文摘要
Abstract
謝誌
目錄
第一章 緒論
第二章 環氧丙烷的不對稱開環反應
第三章 實驗部份
參考文獻
附錄一 化合物之核磁共振光譜圖
附錄二 HPLC分析之原始圖譜

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