Studying computationally anion-π interactions for the first time in asymmetric catalysis: squaramide-catalyzed Henry reactions

Resumen del trabajo presentado al 8th European Symposium on Computing π-Conjugated Compounds (CpiC), celebrado en Málaga (España) del 27 al 28 de enero de 2017.In our search for more efficient organocatalysts, we focus on designing molecules that are able to interact with substrates through non-covalent interactions that are not usually considered in organocatalysis. The trifunctional catalyst represented in the figure, which contains different functional groups capable of forming π-interactions with the substrates, was used in the Henry reaction. The mechanistic studies suggest the formation of different types of π-interactions, such as π-anion and π-hydrogen interactions, which promote reactions that are faster and more selective when compared to those performed with catalysts that only form hydrogen bonds with the substrates. Notably, this study was the second example in which π-anion interactions have been reported in asymmetric organocatalysis, opening new possibilities in this challenging field. Herein, we will present experimental results as well as theoretical calculations that support our hypothesis.Peer reviewe