臺灣博碩士論文加值系統

二,三雙取代的苯駢[b]&;#22139;吩經由末端炔類與二-碘硫代苯甲醚透過鈀催化與親電性環合反應，可以得到良好的產率是已經被報導出來的。
　　我們發展一個新的合成路徑，利用三步一鍋化反應得到苯駢[b]&;#22139;吩的衍生物，在不需要配位基與鈀金屬，只用氯化銅當催化劑與環合試劑，不中止反應下，成功的得到良好的產率。

It has been known that 2,3-disubstituted benzo[b]thiophenes have been prepared in excellent yields via coupling of terminal alkynes with commercially available o-iodothioanisole in the presence of a palladium catalyst and subsequent electrophilic cyclization of the resulting o-(1-alkynyl)thioanisole derivatives.
We have developed a new synthetic method that by using copper choride-mediated cascade reactions of Csp2-Csp coupling, intramolecular cyclization, and Csp2-S coupling without using palladium catalyst and any ligand for one-pot three-step syntheses of 2,3-disubstituted benzo[b]thiophenes.

摘要...............................................................................................................i
英文摘要......................................................................................................ii
目錄.............................................................................................................iii
第壹章． 緒論 ............................................................................................1
一. 何謂過度金屬催化交互偶合(cross-coupling)反應?......................2
二. 鈀金屬催化偶合反應的介紹..........................................................3
三. 銅金屬催化偶合反應的介紹 ........................................................7
1. 傳統的銅催化交互偶合反應..................................................7
2. 銅金屬催化碳－碳三鍵交互偶合反應的配位基(Ligand)介紹............................................................................................8
I. Copper-complexes..........................................................11
II. N,N-Chelators................................................................12
III. N,O-Chelators................................................................13
IV. O,O-Chelators................................................................14
四. 苯駢[b]噻吩的介紹.......................................................................15
I. 苯駢[b]噻吩的合成方法................................................15
II. 苯駢[b]噻吩的應用........................................................22
第貳章． 研究目的....................................................................................24
第參章． 實驗結果與討論........................................................................26
C-C三鍵偶合反應
　 一、背景..............................................................................................26
　 二、尋找最佳化條件..........................................................................28
1. 氯化銅與配位基比例的影響...............................................28
2. 銅種類對於反應的影響.......................................................30
3. 溶劑對於反應的影響...........................................................31
4. 鹼對於反應的影響...............................................................33
5. 親核基與親電子基之比例對於反應的影響.......................34
6. 溫度對於反應的影響...........................................................35
7. 時間對於反應的影響...........................................................36
8. 探究鹵素芳香族及末端炔之交互偶合反應.......................37
兩步一鍋化分子內環合反應
一、背景..............................................................................................43
二、尋找最佳化條件..........................................................................45
9. 針對環合反應氯化銅的量對於反應的影響.......................45
10. 碘化鉀的量對於反應的影響...............................................46
11. 乙腈的量對反應的影響.......................................................47
12. 反應時間對反應的影響.......................................................48
13. 反應溫度對反應的影響.......................................................49
14. 探究不同炔類的環合反應...................................................50
三步一鍋化反應的應用
一、背景..............................................................................................53
15. 探究不同硫醇的偶合反應...................................................55
第肆章． 結論與展望................................................................................59
第伍章． 實驗步驟與光譜資料................................................................60
第陸章． 儀器設備及試劑........................................................................86
第柒章． 參考文獻....................................................................................88
第捌章． NMR光譜資料..........................................................................93













圖表目次
C-C鍵交互偶和反應
Table 1、氯化銅與配位基比例的影響................................................... 28
Table 2、銅種類對於反應的影響............................................................30
Table 3、溶劑對於反應的影響................................................................31
Table 4、鹼對於反應的影響....................................................................33
Table 5、親核基與親電子基之比例對於反應的影響............................34
Table 6、溫度對於反應的影響................................................................35
Table 7、時間對於反應的影響................................................................36
Table 8、探究鹵素芳香族及末端炔之交互偶合反應............................37
兩步一鍋化分子內環合反應
Table 9、針對環合反應氯化銅的量對於反應的影響............................45
Table 10、碘化鉀的量對於反應的影響..................................................46
Table 11、乙睛的量對反應的影響..........................................................47
Table 12、反應時間對反應的影響..........................................................48
Table 13、反應溫度對反應的影響..........................................................49
Table 14、探究不同炔類的環合反應......................................................50
三步一鍋化反應的應用
Table 15、探究不同硫醇的偶合反應......................................................57

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