Häring Marleen, Pérez-Madrigal Maria M, Kühbeck Dennis, Pettignano Asja, Quignard Françoise, Díaz David Díaz
Institute of Organic Chemistry, University of Regensburg, Universitätsstr. 31, Regensburg 93053, Germany.
Institute Charles Gerhardt Montpellier-UMR 5253 CNRS-UMII-ENSCM-UMI, Matériaux Avancés pour la Catalyse et la Santé, 8 rue de l'École Normale, 34296 Montpellier Cedex 5, France.
Molecules. 2015 Mar 4;20(3):4136-47. doi: 10.3390/molecules20034136.
In this manuscript we report a critical evaluation of the ability of natural DNA to mediate the nitroaldol (Henry) reaction at physiological temperature in pure water. Under these conditions, no background reaction took place (i.e., control experiment without DNA). Both heteroaromatic aldehydes (e.g., 2-pyridinecarboxaldehyde) and aromatic aldehydes bearing strong or moderate electron-withdrawing groups reacted satisfactorily with nitromethane obeying first order kinetics and affording the corresponding β-nitroalcohols in good yields within 24 h. In contrast, aliphatic aldehydes and aromatic aldehydes having electron-donating groups either did not react or were poorly converted. Moreover, we discovered that a number of metal-free organic buffers efficiently promote the Henry reaction when they were used as reaction media without adding external catalysts. This constitutes an important observation because the influence of organic buffers in chemical processes has been traditionally underestimated.
在本论文中，我们报道了对天然DNA在纯水中生理温度下介导硝基醇（亨利）反应能力的关键评估。在这些条件下，未发生背景反应（即无DNA的对照实验）。带有强或中等吸电子基团的杂芳醛（如2-吡啶甲醛）和芳醛与硝基甲烷反应良好，遵循一级动力学，在24小时内以良好产率得到相应的β-硝基醇。相比之下，脂肪醛和具有供电子基团的芳醛要么不反应，要么转化率很低。此外，我们发现，当用作反应介质而不添加外部催化剂时，许多无金属有机缓冲剂能有效促进亨利反应。这是一项重要的发现，因为有机缓冲剂在化学过程中的影响传统上一直被低估。
