Author: |
簡子強 Chien, Tzu-Chiang |
---|---|
Thesis Title: |
I. 路易斯酸輔佐六員環2‒烯‒, 2‒炔‒炔醯胺化合物的環化反應:稠雙環δ‒內醯胺化合物的合成 II. 三氯化金催化炔醯胺呋喃化合物的環化反應:吡咯化合物的合成 I. Lewis acid-Promoted Cyclization Reactions of Six-Membered Ring 2‒Ene‒ and 2-Yne-Ynamides:Synthesis of Fused Bicyclic δ-Lactams II. Gold(III) Chloride-Catalyzed Cyclization Reactions of Ynamide-Tethered Furans:Synthesis of pyrroles |
Advisor: |
葉名倉
Yeh, Ming-Chang |
Degree: |
碩士 Master |
Department: |
化學系 Department of Chemistry |
Thesis Publication Year: | 2018 |
Academic Year: | 106 |
Language: | 中文 |
Number of pages: | 347 |
Keywords (in Chinese): | 分子內環化反應 、炔醯胺分子 、三氟化硼乙醚 、稠雙環δ -內醯胺 、六氫異喹啉酮衍生物 、三氯化金 |
Keywords (in English): | intramolecular cyclization, ynamide, BF3.OEt2, fused-bicyclic δ-lactam, gold(III) chloride |
DOI URL: | http://doi.org/10.6345/THE.NTNU.DC.051.2018.B05 |
Thesis Type: | Academic thesis/ dissertation |
Reference times: | Clicks: 127 Downloads: 10 |
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本論文分成二個部分。第一部分是利用三氟化硼乙醚輔佐下第三丁基矽醚保護的2-(乙炔胺)-甲基環己烷-2-烯醇化合物進行分子內環化反應,可得到六氫異喹啉酮衍生物。利用氯化亞鐵輔佐六員環2-炔-炔醯胺化合物進行分子內環化反應,可得到稠雙環δ-內醯胺衍生物。第二部分為利用三氯化金催化5-甲基-2-(乙炔胺)呋喃化合物進行分子內環化反應,可得到吡咯衍生物。
第一部分為三氟化硼乙醚輔佐第三丁基二甲基矽醚保護的2-(乙炔胺)甲基環己烷-2-烯醇化合物進行分子內環化反應,可以直接合成出六氫異喹啉酮衍生物,利用DBU可以將非鏡像異構物的六氫異喹啉酮混合物進行差向異構化(epimerization),得到單一非鏡像異構物。
合成具三個立體中心含鹵素稠雙環δ-內醯胺衍生物,在乾燥空氣及四氫呋喃條件下,利用氯化亞鐵合成含鹵素稠雙環δ-內醯胺衍生物。此反應的優點為起始物合成步驟簡短、實驗操作簡單、不用加入額外的氧化劑且在溫和條件下進行反應。
第二部分為在毒性較低的甲苯及室溫條件下,利用三氯化金催化使炔醯胺呋喃化合物轉變成吡咯衍生物,其優點為條件溫和、實驗操作簡單和不錯的產率。
The thesis cantains two topics. The first part covers the synthesis of hexahydroisoquinolinone derivatives via BF3·OEt2-assisted intramolecular cyclization of alkyl- or aryl-substituted of TBS-protected 2-(ethynyl(tosyl)amino)-methylcyclohex-2-enols and the synthesis of fused-bicyclic δ-lactams via FeCl2-assisted intramolecular cyclization of six-membered yne-ynamide. The second part is the synthesis of pyrrole derivatives via gold(III) chloride-catalyzed intramolecular cyclization of 5-methyl-2-(ethynyl(tosyl)amino)methylfurans.
The BF3·OEt2-assisted intramolecular cyclization of alkyl- or aryl-substituted of TBS-protected 2-(ethynyl(tosyl)amino)-methylcyclohex-2-enols enables a straightforward approach to hexahydroisoquinolinone derivatives. Upon epimerization with 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), the mixture of diastereomers lead to hexahydroisoquinolinone derivatives as a single isomer.
A synthesis of halogenated fused-bicyclic δ-lactams with three stereogenic centers is developed. Treatment of iron(II) chloride with six-membered ring 2-yn-ynamides in THF under dry air afforded halogenated bicyclic δ-lactams in good yields. The reaction are procedurally simple, producing halogenated bicyclic δ-lactams under mild conditions without an additional oxidizing agent.
Gold(III) chloride-catalyzed reaction of 5-methyl-2-(enthynyl(tosyl)amino)methylfuran occurred efficiently in toluene at room temperature, leading to a series of pyrrole derivatives
The advantages of the reactions are mild reaction conditions、simple experimental operations and high yields.
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