研究生: |
徐筱茹 Hsiao-Ju Hsu |
---|---|
論文名稱: |
一、含氮雙烯炔分子內Diels-Alder環化反應:六氫苯[cd]吲哚的合成 二、三氟化硼輔佐3-(5-芳香基-4-戊炔基)環己-2-烯-1-矽醚分子內環化反應:含氟螺旋[4.5]癸烯衍生物的合成 1. Intramolecular Diels-Alder Reactions of Azadienynes: Synthesis of Hexahydrobenzo[cd]indoles 2. BF3-Assisted Synthesis of Fluorinated Carbospirocycles from TBS-Protected 3-(5-Arylpent-4-yn-1-yl)cyclohex-2-en-1-ols |
指導教授: |
葉名倉
Yeh, Ming-Chang |
學位類別: |
碩士 Master |
系所名稱: |
化學系 Department of Chemistry |
論文出版年: | 2013 |
畢業學年度: | 101 |
語文別: | 中文 |
論文頁數: | 226 |
中文關鍵詞: | Diels-Alder反應 、苯[cd]吲哚 、三氟化硼 、螺旋化合物 、喹啉酮 |
英文關鍵詞: | Diels-Alder reaction, benzo[cd]indole, BF3•OEt2, spirocycle |
論文種類: | 學術論文 |
相關次數: | 點閱:152 下載:4 |
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本論文共分為三個主題,第一部分,利用分子內Diels-Alder反應合成吲哚衍生物,以1-甲苯磺醯炔丙胺基-3-乙烯基環己-2-烯作為起始物,於加熱條件下進行Diels-Alder環化反應,再行氧化反應得到六氫苯[cd]吲哚化合物。第二部分,以三氟化硼做為路易士酸及氟離子來源,輔佐3-(5-芳香基-4-戊炔基)環己-2-烯-1-矽醚,進行分子內環化反應,同時生成碳(sp2)-氟單鍵,合成含氟螺旋[4.5]癸烯衍生物。最後以金(I)和銀共催化3-(N,3-二苯丙炔醯胺基)環己-2-烯-1-酮,進行6-endo-dig分子內環化反應,合成二氫喹啉酮衍生物。
This study covers three separated topics. The first work is the synthesis of hexahydrobenzo[cd]indoles via intramolecular Diels-Alder reaction from 1-tosylpropargylamino-3-vinylcyclohex-2-enes. The reaction proceeded via [4+2] cycloaddition followed by oxidation to generate hexahydrobenzo[cd]- indoles. The second part of the thesis is the synthesis of fluorinated spiro[4.5]- decenes from tert-butyldimethyl-silyl-protected 3-(5-arylpent-4-yn-1-yl)cyclo- hex-2-en-1-ols using BF3•OEt2. In this reaction, BF3 reacted as both the Lewis acid and the fluoride source for cyclization/fluorination. The method provided an easy access to spirocyclic skeletons with concomitant formation of a C(sp2)−F bond. Finally, the gold(I)-catalyzed intramolecular cycloisomeri- zation of the 3-(N,3-diphenylpropiolamido)cyclohex-2-en-1-one proceeded through a cationic gold intermediate to afford a dihydroquinolinone. The reaction underwent an endo-dig cyclization to generate an iminium intermedi- ate followed by deprotonation/protodeauration to give a dihydroquinolinone and regenerate the Au(I) catalyst into the catalytic cycle.
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