臺灣博碩士論文加值系統

我們將本實驗室所開發的手性硫化物應用在不對稱環丙烷化反應，經過溶劑、鹼、添加劑、溫度與催化劑的條件優化。其中溶劑與溫度對此反應的反應性與立體選擇性影響最為重要。最後將桂皮基溴與不同推拉電子的查爾酮經由Corey-Chaykovsky 反應，可以得到主要為順式的乙烯基環丙烷並高達95%的鏡像超越值。
另外我們以delta-戊內酯作為起始物，經過六步合成步驟。其中關鍵步驟利用Sharpless 不對稱二羥基化反應建立此化合物的手性中心，可達鏡像超越值99%，最後總產率61%完成新的呋喃化合物。

This work describles catalytic and asymmetric cyclopropanation by using (Thiolan-2-yl)diarylmethanol benzyl ether as an organocatalyst. We optimized the reaction condition by screening solvents, bases, additives, temperatures and catalysts. The most important factors are solvent and temperature, which affect the diastereoselectivity and enantioselectivity. Under the optimized reaction conditions, cinnamyl bromide reacted with trans-chalcones via the CoreyChaykovsky reaction to give major cis-vinylcyclopropanes with up to 95% ee.
Besides, we synthesized a chiral furan compound. It was synthesized from -valerolactone through six steps in 61% total yield. The key step is using asymmetric Sharpless dihydroxylation reaction to build the stereogenetic center of the furan ligand with 99% ee.

中文摘要 I
ABSTRACT II
謝誌 III
縮寫表 IV
目錄 VI
圖目錄 XVII
表目錄 XVIII
式目錄 XIX
第一章 不對稱環丙烷化反應 1
第一節 緒論 1
1-1 環丙烷 (CYCLOPROPANE) 1
1-1-1 環丙烷化反應 (cyclopropanation) 1
1-1-2 利用硫偶極體進行不對稱環丙烷化反應 8
1-1-3 環丙烷化反應之應用 12
1-2 配位基(S)-DIPHENYL(TETRAHYDROTHIOPHEN-2-YL)METHANOL簡介 13
1-2-1 (R)-diphenyl(tetrahydrothiophen-2-yl)methanol合成路徑及應用 14
1-2-2 (S)-THTOH 合成路徑及應用 17
1-3 實驗動機 19
第二節 結果與討論 22
2-1 硫化物5及其衍生物6A-F的合成 22
2-2 不對稱環丙烷化反應之探討 24
2-2-1 環丙烷化反應之溶劑的篩選 24
2-2-2 環丙烷化反應之鹼的篩選 27
2-2-3 環丙烷化反應之添加劑的篩選 28
2-2-4 環丙烷化反應之溫度的篩選 29
2-2-5環丙烷化反應之催化劑的篩選 31
2-2-6 以硫化物做催化劑對不同查爾酮進行不對稱環丙烷反應 33
2-2-7 不對稱乙烯基環丙烷產物非鏡像異構物的鑑定 36
2-2-8 反應機構探討 38
第二章 硫化物(R)-5與手性呋喃化合物的開發 42
第一節 緒論 42
1-1 研究動機 42
第二節 結果與討論 43
2-1 (R)-DIPHENYL(TETRAHYDROTHIOPHEN-2-YL)METHANOL 5的合成 43
2-2 手性呋喃催化劑的合成 46
2-3手性呋喃化合物應用於DIELS-ALDER 反應 48
第三章 結論 50
第四章 實驗及光譜數據 51
GENERAL INFORMATION 51
PROCEDURE FOR SYNTHESIS OF (S)-DIPHENYL(TETRAHYDROTHIOPHEN-2-YL)METHANOL DERIVATIVES 52
GENERAL PROCEDURE FOR SYNTHESIS OF TRANS-CHALCONE (7B-P) 60
GENERAL PROCEDURE FOR SYNTHESIS OF ENANTIOSELECTIVE CYCLOPROPANATION (8A-8P) 67
SYNTHESIS OF (R)-DIPHENYL(TETRAHYDROFURAN-2-YL)METHANOL 89
第五章 參考文獻 96
附錄 99

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