Decoding the impact of solvents in altering the conversion rates and stereoselectivity in proline-catalyzed asymmetric aldol reaction

IF 1.6 4区 化学 Q4 CHEMISTRY, PHYSICAL
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Abstract

The choice of solvent plays a crucial role in aldol reactions, often affecting both the conversion rate and stereoselectivity. In this study, we investigated the influence of solvents (water, methanol and hydroalcoholic) on the proline-catalyzed aldol reactions. We focused on elucidating the solute–solvent interactions at the rate-determining step and the stereoselective step. Our theoretical finding suggests, hydroalcoholic-mediated reaction exhibits a higher conversion rate as compared to pure water and pure methanol-mediated system with the generation of most stable transition state structure. This can be attributed to the existence of strong hydrogen bonding and the formation of stable six-membered transition state structures in hydroalcoholic-mediated system. In addition to this, our research demonstrates that the choice of solvent plays a crucial role in determining the percentage of enantiomeric excess in the reaction. Theoretical finding suggest that the anti-product is preferentially formed in the presence of water and hydroalcoholic media as solvents. Pure water and hydroalcoholic solvents surprisingly showed a higher enantiomeric excess for the anti-product due to formation of strong hydrogen bonding between reaction moiety and solvents. In contrast, methanol-assisted reactions resulted in a racemic mixture, consistent with experimental observations. Results reported in the present study contribute to the broader understanding of solvent effects in organic reactions and offer valuable insights for the design of organic reactions.

解码溶剂在改变脯氨酸催化不对称醛醇反应的转化率和立体选择性方面的影响
摘要 溶剂的选择在醛醇反应中起着至关重要的作用,通常会影响转化率和立体选择性。在本研究中,我们研究了溶剂(水、甲醇和水醇)对脯氨酸催化的醛醇反应的影响。我们重点阐明了在速率决定步骤和立体选择步骤中溶剂与溶剂之间的相互作用。我们的理论发现表明,与纯水和纯甲醇介导的体系相比,水醇介导的反应具有更高的转化率,并能生成最稳定的过渡态结构。这可归因于水醇介导体系中存在强氢键和形成稳定的六元过渡态结构。此外,我们的研究还表明,溶剂的选择对决定反应中对映体过量的百分比起着至关重要的作用。理论研究结果表明,在水和水醇介质作为溶剂的情况下,反产物会优先形成。由于反应分子和溶剂之间形成了强氢键,纯水和水醇溶剂竟然显示出较高的对映体过量。相比之下,甲醇辅助反应产生的是外消旋混合物,这与实验观察结果一致。本研究报告的结果有助于更广泛地了解有机反应中的溶剂效应,并为有机反应的设计提供了宝贵的见解。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
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来源期刊
Theoretical Chemistry Accounts
Theoretical Chemistry Accounts 化学-物理化学
CiteScore
3.40
自引率
0.00%
发文量
74
审稿时长
3.8 months
期刊介绍: TCA publishes papers in all fields of theoretical chemistry, computational chemistry, and modeling. Fundamental studies as well as applications are included in the scope. In many cases, theorists and computational chemists have special concerns which reach either across the vertical borders of the special disciplines in chemistry or else across the horizontal borders of structure, spectra, synthesis, and dynamics. TCA is especially interested in papers that impact upon multiple chemical disciplines.
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