手性四氫噻吩配位基的合成及其應用在不對稱催化反應之研究

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吳欣怡(Hsin-Yi Wu) 查詢紙本館藏

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化學學系

論文名稱

手性四氫噻吩配位基的合成及其應用在不對稱催化反應之研究
(Studies of Chiral Tetrahydrothiophenes in Asymmetric Catalysis)

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摘要(中)

四氫噻吩衍生物 (S)-diphenyl(tetrahydrothiophen-2-yl)methanol (1) 的合成是以市售5-溴戊酸為起始物，經由五步的合成路徑而得。除此之外，我們將探討 (S)-(1) 於不對稱催化領域的應用，如：不對稱環氧化反應、不對稱烯丙基取代反應。在不對稱環氧化的應用上，最佳可以得到反式產物 (34) 92 % e.e；而不對稱烯丙基烷化卅醚化的應用上，仍有改善的空間。

摘要(英)

A novel chiral tetrahydrothiophene derivative (1) was obtained enantioselectively from commercially available 5-bromopentanoic acid through a 5- step synthetic route. We also demostrated the applications of this chiral ligand in asymmetric sulfur ylide epoxidation and organometallic asymmetric allylic substitution.

關鍵字(中)

★ 不對稱催化
★ 四氫噻吩配位基

關鍵字(英)

★ Asymmetric Catalysis
★ Tetrahydrothiophenes

論文目次

中文摘要 i
ABSTRACT ii
目錄　Table of Contents iii
圖目錄　List of Figures v
表目錄　List of Tables viii
縮寫列表　List of Abbreviations ix
第一章　緒論 1
1-1　配位基 diphenyl(tetrahydrothiophen-2-yl)methanol (1) 簡介 1
1-1-1　(R)-diphenyl(tetrahydrothiophen-2-yl)methanol (1) 合成路徑 1
1-1-2　(S)-diphenyl(tetrahydrothiophen-2-yl)methanol (1) 合成路徑 2
1-1-3　以苯甲醛為起始物進行不對稱烷基化催化反應 3
1-2　環氧化反應 (epoxidation) 5
1-2-1　以硫化物作為催化劑進行環氧化反應 (Sulfide-catalyzed epoxidations) 6
1-2-2　以硫化物催化不對稱環氧化反應 6
1-2-3　天然物合成之應用 9
1-3　過渡金屬催化不對稱烯丙基烷化反應 10
1-3-2 釕金屬錯合物催化不對稱烯丙基反應 12
第二章　結果與討論 14
2-1　配位基 (ligand) (S)-(1) 的合成 14
2-1-1　逆合成分析 15
2-1-2　配位基 (S)-(1) 的製備 16
2-2　不對稱硫化物催化環氧化反應之應用 22
2-2-1　將配位基 (1) 應用於不對稱環氧化反應 22
2-2-2　製備配位基 (S)-2-(methoxydiphenylmethyl)tetrahydrothiophene (20) 27
2-2-3　製備配位基 (S)-(diphenyl(tetrahydrothiophen-2-yl)methoxy) trimethylsilane (21) 27
2-2-4　製備配位基 (S)-2-((benzyloxy)diphenylmethyl)tetrahydrothiophene (22) 28
2-2-5　製備配位基 (S)-2-(isopropoxydiphenylmethyl)tetrahydrothiophene (42) 28
2-2-6　製備配位基 (S)-2-(phenoxydiphenylmethyl)tetrahydrothiophene (43) 29
2-3　配位基 (1) 於有機金屬不對稱催化反應上的應用 30
2-3-1　銅錯合物行不對稱烷化反應之選擇性初步研究 30
2-3-2　鈀錯合物進行不對稱烷化卅醚化反應之選擇性初步研究 33
2-3-3　製備可能的錯合物 (58) 及 (60) 34
2-3-4　釕錯合物行不對稱醚化及烷化反應之選擇性初步研究 36
2-3-5　製備配位基 (S)-(diphenyl(tetrahydrothiophen-2-yl)methoxy)　diisopropylphosphine (49) 39
2-3-6　製備配位基 (S)-(diphenyl(tetrahydrothiophen-2-yl)methoxy) diphenylphosphine (50) 40
第三章　結論 41
第四章　實驗及光譜數據 42
4-1　實驗儀器 42
4-2　實驗步驟及光譜數據 44
第五章　參考文獻 69
附錄　Appendixes 77
X-ray crystallographic data of (S)-(1) 78
HPLC analysis 85
1H, 13C and 31P NMR Spectra 91

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指導教授

陳榮傑(Rong-Jie Chein)

審核日期

2012-8-28

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