{"title":"Mechanistic and enantioselectivity analysis of amino acid-catalyzed asymmetric aldol reactions: a theoretical study","authors":"Chao-Xian Yan, Dan-Feng Li, Ling-Jian Yang, Lin-Xing Fu, Xin-Qiang Hua","doi":"10.1007/s11144-025-02799-y","DOIUrl":null,"url":null,"abstract":"<div><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></div>","PeriodicalId":750,"journal":{"name":"Reaction Kinetics, Mechanisms and Catalysis","volume":"138 3","pages":"1923 - 1937"},"PeriodicalIF":1.7000,"publicationDate":"2025-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Reaction Kinetics, Mechanisms and Catalysis","FirstCategoryId":"92","ListUrlMain":"https://link.springer.com/article/10.1007/s11144-025-02799-y","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q4","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
引用次数: 0
Abstract
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.
期刊介绍：
Reaction Kinetics, Mechanisms and Catalysis is a medium for original contributions in the following fields:
-kinetics of homogeneous reactions in gas, liquid and solid phase;
-Homogeneous catalysis;
-Heterogeneous catalysis;
-Adsorption in heterogeneous catalysis;
-Transport processes related to reaction kinetics and catalysis;
-Preparation and study of catalysts;
-Reactors and apparatus.
Reaction Kinetics, Mechanisms and Catalysis was formerly published under the title Reaction Kinetics and Catalysis Letters.
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