樟腦衍生物之γ-醯胺基硫醇與β-氨基醇為掌性配位基的合成與應用

The Synthesis and Application of Camphor Derived Chiral γ-Amido Thiol and β-Amino Alcohol Ligand

沈盈瑩(Ying-Ying Shen)

指導教授 ： 汪炳鈞

國立清華大學/理學院/化學系/碩士(2013年)

https://doi.org/10.6843/NTHU.2013.00095

摘要

本論文以樟腦衍生物之γ-胺基硫醇(-)-MITH (2)、β-氨基醇(+)-MINBOL (3)為主要概念，開發新型的掌性配位基：γ-醯胺基硫醇(10)以及β-氨基醇 (11)。更進一步使用β-氨基醇 (11)為掌性配位基，應用於二乙基鋅以及芳香基鋅試劑對醛類的不對稱加成反應。
在二乙基鋅(1.1 M in toluene)加成反應中僅需0.5 mol % 添加量、在常溫下反應就可得到最高99 %之產率以及最高98 % ee之鏡像選擇性的R組態二級醇產物；在芳香基鋅加成反應中僅需 2.5 mol % 添加量就可得到最高99 % 之產率以及最高90 % ee之鏡像選擇性的雙芳香基甲醇產物。

關鍵字

樟腦衍生物 ； 掌性配位基

並列摘要

This thesis dealt with the development of new chiral ligands, γ-amido thiol (10) and β-amino alcohol (11), based on γ-amino thiol(-)-MITH (2) and β- amino alcohol (+)-MINBOL (3), respectively. Furthermore, this thesis also dealt with the application of β-amino alcohol (11) in catalytic asymmetric addition reactions of diethylzinc and arylzinc to aldehydes to construct chiral secondary alcohols.
Asymmetric ethylation using a stock solution of diethylzinc (1.1 M in toluene) was carried out in the presence of 0.5 mol % of β-amino alcohol (11) at room temperature and the (R)-secondary alcohols with high yields (up to 99 %) and ee values (up to 98 %) were obtained. On the other hand, asymmetric arylation was carried out in the presence of 2.5 mol % of β-amino alcohol (11) and the chiral diarylmethanols with high yields (up to 99 %) and ee values (up to 90 %) were obtained.

參考文獻

12. 鄭楹霓, 碩士論文, 國立清華大學化學系, 2008.

33. 楊博堯, 碩士論文, 國立清華大學化學系, 2010.

30. Wu, K. H.; Zhou, S.; Chen, C. A.; Yang, M. C.; Chiang, R. T.; Chen, C. R.; Gau, H. M. Chem. Commun. 2011, 47, 11668-11670.

31. (a) Wu, P. Y.; Wu, H. L.; Uang, B. J. J. Org. Chem. 2006, 71, 833-835. (b) 吳平宇, 博士論文, 國立清華大學化學系, 2008.

13. (a) Wu, Z. L.; Wu, H. L.; Wu, P. Y.; Uang, B. J. Tetrahedron: Asymmetry 2009, 20, 1556-1560. (b) 吳志龍, 碩士論文, 國立清華大學化學系, 2005.