製備 L-prolinamide 官能基化 SBA-15 的異相鏡像催化劑及其在醛酮間 Aldol 加成反應的應用

SBA-15 supported L-prolinamide as a heterogeneous enantioselective catalyst in aldol reaction between ketone and aldehyde

鄭舜竹(Shun-Chu Cheng)

指導教授 ： 鄭淑芬

國立臺灣大學/理學院/化學研究所/碩士(2014年)

https://doi.org/10.6342/NTU.2014.10903

摘要

一系列以不同碳鏈長度連結固定於 SBA-15 介孔材料之L-prolinamide觸媒經由 thiol-ene 反應合成出來，這些觸媒的化學物理性質經由 XRD、N2吸脫附曲線、IR光譜 以及固態 NMR 等技術做鑑定。這些掌性選擇觸媒在催化反應後可經過簡單的過濾與產物分離並重複使用。
所製備的固定於 SBA-15 介孔材料之L-prolinamide觸媒可以在溫和的條件中催化環己烷與對硝基甲醛之間不對稱的 Aldol 加成反應，數個影響催化表現的因素被探討，包括溶劑的種類、當作溶劑的水量、催化劑的量、L-prolinamide 與 SBA-15 之間的碳鏈長度，反應時間和溫度。結果顯示碳鏈愈長，能達到愈高的選擇率，以八碳鏈長連接於SBA-15的L-prolinamide觸媒轉化率可達 66%，選擇率大於 99%，反應時間由 24 小時延長至 48 小時候，轉化率可提高至 76%，且選擇率依然維持於 99%，此外觸媒可重複使用至少三次以上，而催化效果皆不改變。

關鍵字

SBA-15 ； 介孔 ； 脯氨酰胺 ； aldol 反應

並列摘要

A series of SBA-15 materials with different legnths of linker immobilized L-prolinamide catalysts were prepared by thiol-ene reaction. The materials were characterized with XRD, N2 sorption isotherm, IR spectroscopy and solid-state NMR techniques. These catalysts with chiral centers could be reused by simple filtration to separate from the products.
The SBA-15 anchored L-prolinamide could catalyze asymmetric Aldol reaction between cyclohexanone with 4-nitrobenzaldehyde under mild condition. Factors which might affect the catalytic performance including the type of solvents, the amount of water as solvent, the amount of catalysts, the linker length between L-prolinamide and SBA-15, the reaction time and temperature. The results showed that higher enentioselectivity could be reached over the catalysts with longer linker. The catalyst containing octyl chain between SBA-15 and L-prolinamide gave 66% of conversion, and greater than 99% of enantioselectivity. The conversion could be increased to 76% and the the enantioselectivity was still unchanged when the reaction was prolonged from 24 h to 48 h. These catalysts could be reused at least three times retaining the same activities.

並列關鍵字

SBA-15 ； mesoporous ； prolinamide ； aldol reaction

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