Scholarlink

<p>In this work, we theoretically studied the asymmetric aldol reactions between acetone and <i>p</i>-NO<sub>2</sub>PhCHO catalyzed by (<i>S</i>)-proline, (<i>S</i>)-azetidine-2-carboxylic acid, (<i>S</i>)-pipecolic acid, <sub>L</sub>-hisdine, <sub>L</sub>-phenylalanine, <sub>L</sub>-valine and N-methyl-<sub>L</sub>-valine. For all reactions, the potential Gibbs energy surfaces are drawn after DFT calculations, and the rate-determining steps are determined. Both thermodynamics and kinetics can influence the yield of the main reactions, the side reactions are suppressed by either thermodynamics or kinetics, and the enantioselectivity difference between the (<i>S</i>)-proline- and (<i>S</i>)-azetidine-2-carboxylic acid-catalyzed reactions is determined by the difference in the entropy effect between the stereo-determining transition states, which is investigated by different DFT-D methods.</p>

错误：搜索内容不能为空，请输入英文关键词
错误：关键词超出字数限制，请精简
高级检索

Mechanistic and enantioselectivity analysis of amino acid-catalyzed asymmetric aldol reactions: a theoretical study

  • 期刊论文

  • 发表日期：

    2025年1月13日

查看全文
  • Chao-Xian Yan,
  • Dan-Feng Li,
  • Ling-Jian Yang,
  • Lin-Xing Fu,
  • Xin-Qiang Hua

摘要

In this work, we theoretically studied the asymmetric aldol reactions between acetone and p-NO2PhCHO catalyzed by (S)-proline, (S)-azetidine-2-carboxylic acid, (S)-pipecolic acid, L-hisdine, L-phenylalanine, L-valine and N-methyl-L-valine. For all reactions, the potential Gibbs energy surfaces are drawn after DFT calculations, and the rate-determining steps are determined. Both thermodynamics and kinetics can influence the yield of the main reactions, the side reactions are suppressed by either thermodynamics or kinetics, and the enantioselectivity difference between the (S)-proline- and (S)-azetidine-2-carboxylic acid-catalyzed reactions is determined by the difference in the entropy effect between the stereo-determining transition states, which is investigated by different DFT-D methods.