- 學位論文
1,1'-聯-2-萘酚與鋁或銦離子形成之錯合物催化醛或酮的不對稱反應研究
Asymmetric Reactions of Aldehydes or Ketones Catalyzed by Aluminum(III) and Indium(III) Complexes with 1,1'-Bi-2-naphthol(BINOL) as Chiral Ligand
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摘要
本論文研究包含三個部份：第一部份是利用1,1’-聯-2-萘酚(BINOL)作為掌性配位基與鋁離子形成錯合物催化芳香酮的不對稱硼烷還原反應研究；第二部份是利用1,1’-聯-2-萘酚(BINOL)作為掌性配位基與銦離子形成錯合物催化醛類的不對稱烯丙基化反應研究；第三部份是利用1,1’-聯-2-萘酚(BINOL)作為掌性配位基與銦離子形成錯合物催化芳香酮的不對稱矽烷還原反應研究。 ㄧ、在不對稱硼烷還原反應方面，利用BINOL作為掌性配位基與Al(OiPr)3組成催化系統還原芳香酮類，反應過程方便快速，最高可獲得83%的鏡像超越值，我們也推測了可能的反應機構並用以解釋所得產物的立體化學組態。 二、在不對稱烯丙基化反應方面，以BINOL作為掌性配位基與三溴化銦形成的錯合物，可以催化烯丙基三甲氧基矽烷對醛類化合物的加成反應，得到的二級醇產物具有中等鏡像選擇性，最高可獲得58%的鏡像超越值。 三、在不對稱矽烷還原反應方面，以BINOL作為掌性配位基與In(OTf)3形成的錯合物，用在催化三甲氧基矽烷對芳香酮化合物的還原反應中，所得的二級醇產物只有偏低的鏡像選擇性；由反應機構的推導我們認為若是可以除去反應中的矽鹵化物，有機會改善還原反應的立體選擇性。
並列摘要
The studies on the asymmetric reactions of aldehydes or ketones catalyzed by Aluminum(III) or Indium(III) complexes with 1,1’-Bi-2-naphthol (BINOL) as chiral ligand are described. This thesis consists of three parts. The first part is concerned with catalytic asymmetric borane reduction of aromatic ketones. Up to 83% ee could be obtained with 10 mol% Al(OiPr)3/BINOL2 complex as catalyst. The second part is about catalytic asymmetric allylation of aldehydes by allyltrimethoxysilane. Moderate yields and ees could be achieved with InBr3/BINOL complex as catalyst. In the third part, In(OTf)3/BINOL was conducted into the asymmetric silane reduction of aromatic ketones as catalyst, and only low ees could be obtained. Modification based on the reaction mechanism has been proposed to improve the enantioselectivity.
參考文獻
3. Seyden-penne J. In "Chiral Auxiliaries and Ligands in Asymmetric Synthesis", John-Wiley and sons, New York, 1995.
6. (a) Davis, F. A.; Chen, B.-C. Chem. Rev. 1992, 92, 919. (b) Davis, F. A.; Chen, B.-C. J. Org. Chem. 1993, 58, 1751.
11. Brunel, J. M. Chem. Rev. 2005, 105, 857.
12. Cooke, A. S.; Harris, M. M. J. Chem. Soc. 1963, 2365.
14. Nishizawa, M.; Yamada, M.; Noyori, R. Tetrahedron Lett. 1981, 22, 247.
延伸閱讀
- Lee, S. J., & Chen, C. T. (1980). 蒽及2－甲基萘之提取及2－甲基萘之氧化反應. 中央研究院化學研究所集刊, (27), 7-12. https://doi.org/10.6522/BICAS.1980.27.2
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- 陳許志勇（2011）。仿生不對稱銅催化劑對萘酚與其衍生物進行具鏡像選擇性氧化偶合反應之研究〔碩士論文，國立臺灣師範大學〕。華藝線上圖書館。https://www.airitilibrary.com/Article/Detail?DocID=U0021-1610201315242485
- 周益邦（2005）。Syntheses and mesomorphic properties of bent-shaped molecules derived from 4,4’-thiodiphenol and 4,4’-sulfonyldiphenol as the central units〔碩士論文，淡江大學〕。華藝線上圖書館。https://www.airitilibrary.com/Article/Detail?DocID=U0002-0509200513272000
- 陳彥臻（2013）。I. Synthesis of Aluminum Complexes with Ketimine Ligands, and Their Application in the Ring-Opening Polymerization of ε-Caprolactone.II. Synthesis of Copper Complexes with NHC Carbene Ligands, and Their Application in the C-S Coupling and Click reaction.〔碩士論文，高雄醫學大學〕。華藝線上圖書館。https://www.airitilibrary.com/Article/Detail?DocID=U0011-1107201313270300