Stereoselectivities in α- and β-Amino Acids Catalyzed Mannich Reactions Involving Cyclohexanone

高等学校化学研究 ›› 2011, Vol. 27 ›› Issue (4): 673-677.

Stereoselectivities in α- and β-Amino Acids Catalyzed Mannich Reactions Involving Cyclohexanone

WANG Ying, FU Ai-ping*, LI Hong-liang, TIAN Feng-hui, YUAN Shu-ping, SI Hong-zong, DUAN Yun-bo and WANG Zong-hua

Institute for Computational Science and Engineering, Laboratory of New Fiber Materials and Modern Textile, Growing Base for State Key Laboratory, College of Chemical and Environmental Engineering, Qingdao University, Qingdao 266071, P. R. China

收稿日期:2010-11-26 修回日期:2011-01-24 出版日期:2011-07-25 发布日期:2011-06-29
通讯作者: FU Ai-ping E-mail:faplhl@eyou.com
基金资助:
Supported by the National Natural Science Foundation of China(Nos.20773071, 20901043), the Natural Science Foundation of Shandong Province, China(No.ZR2010BM024) and the Project of Shandong Province Higher Educational Science and Technology Program, China(No.J10LB06).

Stereoselectivities in α- and β-Amino Acids Catalyzed Mannich Reactions Involving Cyclohexanone

WANG Ying, FU Ai-ping*, LI Hong-liang, TIAN Feng-hui, YUAN Shu-ping, SI Hong-zong, DUAN Yun-bo and WANG Zong-hua

Institute for Computational Science and Engineering, Laboratory of New Fiber Materials and Modern Textile, Growing Base for State Key Laboratory, College of Chemical and Environmental Engineering, Qingdao University, Qingdao 266071, P. R. China

Received:2010-11-26 Revised:2011-01-24 Online:2011-07-25 Published:2011-06-29
Contact: FU Ai-ping E-mail:faplhl@eyou.com
Supported by:
Supported by the National Natural Science Foundation of China(Nos.20773071, 20901043), the Natural Science Foundation of Shandong Province, China(No.ZR2010BM024) and the Project of Shandong Province Higher Educational Science and Technology Program, China(No.J10LB06).

摘要/Abstract

摘要： The effects of two different amino acid catalysts on the stereoselectivities in the direct Mannich reactions of cyclohexanone, p-anisidine and p-nitrobenzaldehyde were studied with the aid of density functional theory. Transition states of the stereo-determining C―C bond-forming step with the addition of enamine intermediate to the imine for the L-proline(α-amino acid) and (R)-3-pyrrolidinecarboxylic acid(β-amino acid)-catalyzed processes were reported. B3LYP/6-31G** calculations provide a good explanation for the opposite syn vs. anti diastereoselectivities of these two different kinds of catalysts(syn-selectivity for the α-amino acid catalysts, anti-selectivity for the β-amino acid catalysts). Calculated and observed diastereomeric ratio and enantiomeric excess values are in reasonable agreement.

关键词: Syn- and anti-Mannich reaction, Stereoselectivity, Amino acid, Transition state

Abstract: The effects of two different amino acid catalysts on the stereoselectivities in the direct Mannich reactions of cyclohexanone, p-anisidine and p-nitrobenzaldehyde were studied with the aid of density functional theory. Transition states of the stereo-determining C―C bond-forming step with the addition of enamine intermediate to the imine for the L-proline(α-amino acid) and (R)-3-pyrrolidinecarboxylic acid(β-amino acid)-catalyzed processes were reported. B3LYP/6-31G** calculations provide a good explanation for the opposite syn vs. anti diastereoselectivities of these two different kinds of catalysts(syn-selectivity for the α-amino acid catalysts, anti-selectivity for the β-amino acid catalysts). Calculated and observed diastereomeric ratio and enantiomeric excess values are in reasonable agreement.

Key words: Syn- and anti-Mannich reaction, Stereoselectivity, Amino acid, Transition state

WANG Ying, FU Ai-ping*, LI Hong-liang, TIAN Feng-hui, YUAN Shu-ping, .... Stereoselectivities in α- and β-Amino Acids Catalyzed Mannich Reactions Involving Cyclohexanone[J]. 高等学校化学研究, 2011, 27(4): 673-677.

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Stereoselectivities in α- and β-Amino Acids Catalyzed Mannich Reactions Involving Cyclohexanone

Stereoselectivities in α- and β-Amino Acids Catalyzed Mannich Reactions Involving Cyclohexanone

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