噁噻硼烷－氯化鎵錯合物催化不對稱 Diels-Alder 反應之研究

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姓名

蔡玫伶(Mei-Ling Tsai) 查詢紙本館藏

畢業系所

化學學系

論文名稱

噁噻硼烷－氯化鎵錯合物催化不對稱 Diels-Alder 反應之研究
(Oxathiaborolium Gallium Chloride Complexes Catalyzed Asymmetric Diels-Alder Reactions)

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摘要(中)

以市售的5-溴基戊酸乙酯為起始物經由四步驟可以得到手性硫化物5a-c。另外，利用市售的苯并噻吩作為起始物，經由六步驟後合成具有光學活性的硫化物5d。硫化物5a-d 在三氯化鎵的幫助下合成出新穎的噁噻硼烷－氯化鎵錯合物18a-d，成功將其應用在不對稱Diels-Alder 催化反應得到不錯的產率及鏡像選擇性。

摘要(英)

The chiral tetrahydrothiophene derivatives 5a-c were synthesized from commercially available 5-bromovalerate in 4 steps and the chiral dihydrobenzothiophene derivatives 5d was synthesized from commercially available benzothiophene in 6 steps. We successfully synthesized a novel oxathiaborolium using gallium trichloride as the halophile, and successfully applied it in catalystic and asymmetric Diels-Alder reactionin excellent yield with high stereoselectivity.

關鍵字(中)

★ Diels-Alder反應
★ 噁噻硼烷

關鍵字(英)

論文目次

中文摘要 ..................................................................................................................................... i
Abstract ....................................................................................................................................... ii
誌謝 ........................................................................................................................................... iii
目錄 ........................................................................................................................................... iv
圖目錄 ....................................................................................................................................... vi
表目錄 ...................................................................................................................................... vii
符號說明 ................................................................................................................................. viii
第一章緒論 ........................................................................................................................ 1
1-1 Diels-Alder 反應 .................................................................................................... 1
1-2 Diels-Alder 反應在合成上的應用 ........................................................................ 3
1-3 Borenium ion .......................................................................................................... 7
第二章結果與討論 .......................................................................................................... 10
2-1 手性硫化物 .......................................................................................................... 10
2-1-1 手性硫化物5a-b 的製備 ......................................................................... 10
2-1-2 手性硫化物5c 的製備 ............................................................................ 12
2-1-3 手性硫化物5d 的製備 ............................................................................ 13
2-2 不對稱Diels-Alder 反應 ..................................................................................... 15
2-2-1 合成噁噻硼烷催化劑 .............................................................................. 15
2-2-2 親鹵試劑之篩選 ...................................................................................... 17
2-2-3 手性硫化物之篩選 .................................................................................. 21
2-2-4 以不同的親二烯體進行不對稱Diels-Alder 反應 ................................. 23
2-2-5 反應機構 .................................................................................................. 25
2-2-6 以催化劑18 進行Mukaiyama Michael Addition ................................... 26
第三章結論 ...................................................................................................................... 28
第四章實驗部分 .............................................................................................................. 29
4-1 General Information ............................................................................................. 29
4-2 Procedures and Spectroscopic Data ...................................................................... 30
第五章參考文獻 .............................................................................................................. 41
附錄 .......................................................................................................................................... 44

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指導教授

陳榮傑、謝發坤(Rong-Jie Chein Fa-Kuen Shieh)

審核日期

2016-7-27

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