Author: |
劉軒如 Liu, Syuan-Ru |
---|---|
Thesis Title: |
一、對掌樟腦架構衍生之α-重氮羰基輔助劑於不對N-H鍵嵌入反應之探討 二、有機催化Michael加成反應在製備掌性四級碳化合物之探討 1.The Studies of N-Phenyl Camphorpyrazolidinone Derived a-Diazocarbonyl in Diastereoselective N-H Insertion Reaction 2. Asymmetric Organocatalytic Michael Reaction for the Synthesis of Quaternary Carbon-Containing Compounds |
Advisor: |
陳焜銘
Chen, Kwun-Min |
Degree: |
碩士 Master |
Department: |
化學系 Department of Chemistry |
Thesis Publication Year: | 2010 |
Academic Year: | 98 |
Language: | 中文 |
Keywords (in Chinese): | 不對稱合成 、重氮 |
Keywords (in English): | diazo |
Thesis Type: | Academic thesis/ dissertation |
Reference times: | Clicks: 81 Downloads: 0 |
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本論文共分兩大部分:第一部分探討非鏡像選擇性之胺化反應,第二部分則探討鏡像1,4-加成反應。第一部分以本實驗室合成之對掌輔助劑110進行修飾,製備α-重氮羰基對掌輔助劑起始物123,在室溫下,以二氯甲烷為作為反應溶劑,與各種胺類受質124及5 mol%之二價銠金屬催化劑進行不對稱N-H鍵嵌入反應,可得到最佳產率(65%)及非鏡像選擇性(88:12),產物分子經由核磁共振光譜分析及X光單晶繞射確定新建構之立體中心構形為R。另外,可成功將對掌輔助劑110切除回收,得到98%之對掌輔助劑及80%的胺基醇化合物131e。
第二部分利用本實驗室所開發之含有樟腦分子架構之L-脯胺酸有機催化劑230催化β-硝基苯乙烯類起始物136、147及α,α-不同取代之醛類起始物198、228進行不對稱Michael加成反應,篩選出以-硝基苯乙烯136及4當量的2-苯基丙醛228為起始物,在室溫下,以甲醇為反應溶劑,以20 mol%的催化劑進行反應時,得到最佳之產率(62%)、非鏡像選擇性(88:12)及鏡像超越值(52%)。
This dissertation was divided into two parts, they are as follows: The first part represents to study the chiral auxiliary mediated diastereoselective N-H insertion by using the modified derivative from N-phenyl camphorpyrazolindione (110). The reaction was carried out in CH2Cl2 at ambient temperature, by using the α-diazocarbonyl compound (123) as the starting material and catalytic amount of rhodium acetate (5 mol%) generate metallocarbene intermediate. This was followed by addition of amine source (124). In this process N-H insertion products were obtained in high yield up to 65% yield and with up to 88:12 diastereoselectivity. The newly generated chiral center of the major product shows R configuration was confirmed by H-NMR studies and X-ray crystallographic data. On the other hand, the chiral auxiliary was successfully removed, and the recovered yield of 110 up to 98% and amino alcohol 131e was obtained in 80% yield.
In the second part, the Michael additoion ofα,α-disubstituted aldehydes (198, 228) to β-nitroalkenes (136, 147) have been developed. The Michael addition is efficiently catalyzed by the pyrrolidin-camphor derivative (230) as bifunctional organocatalyst producing Michael adduct in moderate to good yield and stereoselectivities. The reaction was carried out in MeOH under room temperature by using β-nitrostyrene and 4 equivalents of donor aldehyde as starting material and 20 mol% of catalyst 230. The Michael adduct achieved with best result is 62% yield with 88:12 diastereoselectivity and 52% enantioselectivity.
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