Citation: Qingying Zhu, Haimin Shen, Zhujin Yang, Hongbing Ji. Biomimetic asymmetric Michael addition reactions in water catalyzed by amino-containing β-cyclodextrin derivatives[J]. Chinese Journal of Catalysis, ;2016, 37(8): 1227-1234. doi: 10.1016/S1872-2067(15)61122-6 shu

Biomimetic asymmetric Michael addition reactions in water catalyzed by amino-containing β-cyclodextrin derivatives

a. School of Chemistry and Chemical Engineering, Sun Yat-sen University, Guangzhou 510275, Guangdong, China;
b. College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310014, Zhejiang, China

Received Date: 11 March 2016
Revised Date: 24 April 2016

Fund Project: This work was supported by the National Natural Science Foundation of China (21425627, 21376279).

Nine β-cyclodextrin derivatives containing an amino group were synthesized via nucleophilic substitution from mono(6-O-p-tolylsulfonyl)-β-cyclodextrin and used in asymmetric biomimetic Michael addition reactions in water at room temperature. The mechanism responsible for the moderate activity and enantioselectivity of the β-cyclodextrin derivatives was explored using nuclear magnetic resonance spectroscopy, namely 2D ¹H rotating-frame overhauser effect spectroscopy (ROESY), ultraviolet absorption spectroscopy, and quantum chemical calculations, which provide a useful technique for investigating the formation of inclusion complexes. The effects of the pH of the reaction medium, the β-cyclodextrin derivative dosage, the structure of the modifying amino group, and various substrates on the yield and enantioselectivity were investigated. The results indicated that these factors had an important effect on the enantiomeric excess (ee) in the reaction system. Experiments using a competitor for inclusion complex formation showed that a hydrophobic cavity is necessary for enantioselective Michael addition. A comparison of the reactions using 4-nitro-β-nitrostyrene and 2-nitro-β-nitrostyrene showed that steric hindrance improved the enantioselectivity. This was verified by the optimized geometries obtained from quantum chemical calculations. An ee of 71% was obtained in the asymmetric Michael addition of cyclohexanone and 2-nitro-β-nitrostyrene, using (S)-2-aminomethylpyrrolidine-modified β-CD as the catalyst, in an aqueous buffer solution, i.e., CH₃COONa-HCl (pH 7.5).
- β-Cyclodextrin,
- Modification,
- Enantioselective Michael addition,
- Quantum chemistry calculation
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沈阳化工大学材料科学与工程学院沈阳 110142