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研究生: 潘麗雪
論文名稱: 一.樟腦衍生物之對掌螯合劑在鏡像炔化加成反應之探討 二.樟腦衍生物之對掌輔助劑在非鏡像氮丙啶上的探討
指導教授: 陳焜銘
學位類別: 碩士
Master
系所名稱: 化學系
Department of Chemistry
論文出版年: 2007
畢業學年度: 95
語文別: 中文
論文頁數: 185
中文關鍵詞: 氮丙啶, 炔化加成
論文種類: 學術論文
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  • 本論文主要分成兩大部分,摘要如下:
    第一部分在探討以樟腦架構雙聚衍生物(114)作為不對稱炔化加成的對掌螯合劑。以苯甲醛為起始物,二乙基鋅為路易士酸進行炔化加成,可以得到R-form的炔丙基醇產物,其產率和鏡像超越值為90%和33%;當化合物114和四異丙醇化鈦在1:4莫耳數比例條件下,作為炔化加成之對掌催化劑,2-naphthaldehyde為起始物可得到50%的產率和86% ee的S-form產物,並利用反應機構解釋立體化學中心反轉之現象。
    第二部份在探討以對掌α,β-不飽和醯胺進行不對稱氮丙啶反應。以N-Tosylcamphorpyrazolidinone為對掌輔助劑,製備α,β-不飽和醯胺衍生物,並以其為起始物,利用N-aminophthalimide和四醋酸鉛進行不對稱氮丙啶反應,可得到22-53%的產率和不錯的非鏡像選擇性(>95:5),產物之絕對立體組態經由X-ray單晶繞射確認。

    The dissertation is divided into two section, they are as follows:
    I. The catalytic asymmetric alkyne addition to carbonyl compounds has attracted intense research activity in recent years because optically active propargylic alcohols are versatile precursors for synthesis of many chiral organic compounds. We have investigated the asymmetric alkynylzinc addition catalyzed by camphor derived 114 and Ti(Oi-Pr)4 and found that this catalyst system is moderate yield (50-95%) and enatioselectivity (19-86% ee). The absolute configuration of the newly generated stereogenic center in the product was determined to have an S-configuration.
    II. Aziridine is three-membered nitrogen-containing heterocycle of great importance as versatile chiral building block in organic synthesis. A new camphor-base chiral auxiliary N-tosylcamphorpyrazolidinone was synthesized, and test as a stereocontrolling element in aziridine reaction across a range of substrates.
    Treatment of N-tosylcamphorpyrazolidinone derived N-enones with N-aminophthalimide and lead tatracetate gave high diastereoselectivity (>95:5). The absolute configuration of the newly generated stereogenic center in product 297 was determined to have an R-configuration, as deduced from a single X-ray crystal analysis.

    中文摘要 英文摘要 一、樟腦衍生物之對掌螯合劑在鏡像炔化加成反應之探討 1.1 序論………………………………………………………………………………1 1.1.1 前言………………………….…………………………………………………2 1.1.2 不對稱炔化加成.………………………………………………………………3 1.1.2.1 利用對掌螯合劑對醛類進行不對稱炔化反應………….………………….3 1.1.2.2 利用對掌螯合劑對其他親電子性試劑進行不對稱炔化加成…………….12 1.1.3 炔化反應在合成上的應用……………………………………………………14 1.1.4 研究動機……………………………………………………………………....15 1.2 結果與討論……………………………………………………………………...16 1.2.1 對掌螯合劑之開發…...………………………………………………...……..16 1.2.2 不對稱炔化加成……………………………....................................................18 1.2.2.1 路易士酸之篩選…………………………...…..............................................18 1.2.2.2 對掌螯合劑之篩選……………………………….........................................21 1.2.2.3 溶劑之效應…………....…………………………………………………….22 1.2.2.4 對掌螯合劑和路易士酸當量數比之影響.....................................................23 1.2.2.5 不同取代基之影響.........................................................................................24 1.2.2.6 路易士酸為二乙基鋅和四異丙醇化鈦之反應機構…………….................26 1.2.3 結論....................................................................................................................28 二、樟腦衍生物之對掌輔助劑在非鏡像氮丙啶上的探討 2.1 序論.......................................................................................................................29 2.1.1 前言....................................................................................................................29 2.1.2 氮丙啶之合成…………………………………………....................................31 2.1.2.1 利用對掌螯合劑進行不對稱氮丙啶反應………….....................................33 2.1.2.2 利用對掌輔助劑進行不對稱氮丙啶反應.....................................................41 2.1.2.3 利用有機催化進行不對稱氮丙啶反應.........................................................43 2.1.3 氮丙啶合成之運用.....................................……………………………..….....46 2.1.4 研究動機……………………............................................................................48 2.2 結果與討論...........................................................................................................49 2.2.1 新對掌輔助劑之開發與合成......................................................................49 2.2.2 對掌α,β-不飽和醯胺之製備..................................................................51 2.2.3 對掌α,β-不飽和醯胺之氮丙啶合成...........................................................54 2.2.3.1 非鏡像選擇性之確認…………….................................................................54 2.2.3.2 溶劑與溫度效應.............................................................................................57 2.2.3.3 取代基效應.....…………………………………………………......………..58 2.2.3.4 氮翻轉異構物(N-invertomers)……………………………………..………59 2.2.3.5 不同對掌輔助劑進行氮丙啶之比較.............................................................60 2.2.3.6 推測反應之機構…………………………………………………...………..61 2.2.3.7 對掌輔助劑的回收再利用………………………….……………..………..62 2.2.4 結論………………….………………………………………...……..………..63 三、實驗步驟與光譜數據 3.1 分析儀器及基本實驗操作…….…………………………………..…..………..64 3.2 對掌螯合劑之製備與步驟………………..…………………………...………..66 3.3 不對稱炔丙基醇之製備與步驟…..…………………………...………………..66 3.4 對掌輔助劑之製備與步驟…………………..……………..…………………...70 3.5 對掌α,β-不飽和醯胺之製備與步驟………………….…………………...........72 3.6 非鏡像氮丙啶化合物之製備與步驟………………...........................................75 四、參考文獻...………………………………………………………………….……79 附錄一 1H及13C-NMR光譜圖……………………………………………....……83 附錄二 X-ray 結構解析與數據.……………………………………………....…..120

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