Organic Chemistry Institute, University of Münster, Corrensstrasse 36, 48149, Münster, Germany.
current address: Institute of Physical Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224, Warsaw, Poland.
Chemistry. 2020 Dec 23;26(72):17598-17603. doi: 10.1002/chem.202003994. Epub 2020 Nov 20.
H-bond donor catalysts able to modulate the reactivity of ionic substrates for asymmetric reactions have gained great attention in the past years, leading to the development of cooperative multidentate H-bonding supramolecular structures. However, there is still a lack of understanding of the forces driving the ion recognition and catalytic performance of these systems. Herein, insight into the cooperativity nature, anion binding strength, and folding mechanism of a model chiral triazole catalyst is presented. Our combined experimental and computational study revealed that multi-interaction catalysts exhibiting weak binding energies (≈3-4 kcal mol ) can effectively recognize ionic substrates and induce chirality, while strong dependencies on the temperature and solvent were quantified. These results are key for the future design of catalysts with optimal anion binding strength and catalytic activity in target reactions.
在过去的几年中，能够调节离子底物反应性的氢键供体催化剂在不对称反应中引起了极大的关注，从而导致了协同多齿氢键超分子结构的发展。然而，对于这些体系中离子识别和催化性能的驱动力仍缺乏了解。本文介绍了一种模型手性三唑催化剂的协同性质、阴离子结合强度和折叠机制的深入了解。我们的实验和计算研究表明，表现出较弱结合能（≈3-4 kcal/mol）的多相互作用催化剂可以有效地识别离子底物并诱导手性，同时定量了对温度和溶剂的强烈依赖性。这些结果对于未来设计在目标反应中具有最佳阴离子结合强度和催化活性的催化剂具有关键意义。
