新型手性N, N, N', N'', N''', N'''-六-[2-(1-羟丁基)]三乙四胺六乙酰胺的合成及其在 不对称氢硅化反应中的应用
Synthesis of Novel Chiral Triethylenetetramine-N, N, N', N'', N''', N'''-hexa-[2-(1-hydroxybutanyl)] acetoamide and Their Application in Asymmetric Hydrosilylation

作者: 李伟杰 :韩山师范学院化学系,潮州;

关键词: 三乙四胺六乙酸N N N' N'' N''' N'''-六-[2-(1-羟丁基)]三乙四胺六乙酰胺合成不对称氢硅化Triethylenetetramine-NNN'N''N'''N'''-hexaacetic Acid Triethylenetetramine-N N N' N'' N''' N'''-hexa-[2-(1-hydroxybutanyl)]acetoamide Synthesis Asymmetric Hydrosilylation

摘要:

在N2保护下,三乙四胺六乙酸分别与(R)- 或(S)-2-氨基-1-丁醇在145℃下反应16 h,合成了新的手性化合物(R)-(+)-或(S)-(-)-N, N, N', N'', N''', N'''-六-[2-(1-羟丁基)]三乙四胺六乙酰胺,产率分别为69.5%和71.3%。运用上述手性化合物与[Rh(COD)Cl]2作手性催化剂,探讨了其在苯乙酮的不对称氢硅化反应中的催化活性,结果显示其具有较明显的催化活性,但反应的对映选择性较低(仅为37%ee)。

Abstract: Triethylenetetramine-N, N, N', N'', N''', N'''-hexaacetic acid reacted with (R)- or (S)-2-amino-1-butanol for 16 h at 145˚C under the protection of nitrogen atmosphere, and gave novel chiral compounds (R)-(+)- or (S)-(-)-triethylenetetramine-N, N, N', N'', N''', N'''-hexa-[2-(1-hydroxybutanyl)] acetoamide in the yields of 69.5% and 71.3%, respectively. With the above chiral compounds and [Rh(COD)Cl]2 as chiral catalysts, the asymmetric hydrosilylation of acetophenone was investigated. The experimental results showed that they had remarkable catalytic activities, but the enantioselectivities of the reaction were low (only 37%ee).

文章引用: 李伟杰 (2014) 新型手性N, N, N', N'', N''', N'''-六-[2-(1-羟丁基)]三乙四胺六乙酰胺的合成及其在 不对称氢硅化反应中的应用。 有机化学研究, 2, 13-17. doi: 10.12677/JOCR.2014.22002

参考文献

[1] Kawasaki, K. and Katsuki, T. (1997) Enantioselective allylic oxidation of cycloalkenes by using Cu(II)-tris(oxazoline) complex as a catalyst. Tetrahedron, 53, 6337-6350.

[2] Kim, S.G. and Ahn, K.H. (2000) Novel artificial receptors for alkylammonium ions with remarkable selectivity and affinity. Chemistry-A European Journal, 6, 3399-3401.

[3] Kim, S.G., Kim, K.H., Jung, J., Shin, S.K. and Ahn, K.H. (2002) Unprecedented chiral molecular recognition in a C3-symmetric environment. Journal of the American Chemical Society, 124, 591-596.

[4] Ann, K.H., Ku, H.Y., Kim, Y., Kim, S.G., Kim, Y.K., Son, H.S. and Ku, J.K. (2003) Fluorescene sensing of ammonium and organoammonium ions with tripodal oxazoline receptors. Organic Letters, 5, 1419-1422.

[5] Zhou, J. and Tang, Y. (2002) Sidearm effect: Improvement of the enantiomeric excess in the asymmetric Michael addition of indoles to alkylidene malonates. Journal of the American Chemical Society, 12, 9030-9031.

[6] Zhou, J. and Tang, Y. (2005) The development and application of chiral trisoxazolines in Asymmetric catalysis and molecular recognition. Chemical Society Reviews, 34, 664-676.

[7] 李伟杰, 许遵乐 (2006) 新型手性多元β-酰胺醇的合成. 化学通报, 12, 937-940.

[8] Zhang, Y.J., Wang, F. and Zhang, W. (2007) Chelation-induced axially chiral palladium complex system with tetraoxazoline ligands for highly enantioselective Wacker-type cyclization. The Journal of Organic Chemistry, 72, 92089213.

[9] Kuang, Y., Sun, X., Chen, H., Liu, P. and Jiang, R. (2009) A novel planar chiral N-heterocyclic carbine-oxazoline ligand for the asymmetric hydrosilylation of ketones. Catalysis Communications, 10, 1493-1496.

[10] Li, W.J., Xu, Z.L. and Qiu, S.X. (2010) Concise methods for the synthesis of chiral polyoxazolines and their application in asymmetric hydrosilylation. Beilstein Journal of Organic Chemistry, 6, 1-9.

分享
Top