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
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2018
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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.
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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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, intramolecular cyclization, ynamide, BF3.OEt2, fused-bicyclic δ-lactam, hexahydroisoquinolinone derivatives, gold(III) chloride