Benz Sebastian, Poblador-Bahamonde Amalia I, Low-Ders Nicolas, Matile Stefan
Department of Organic Chemistry, University of Geneva, Geneva, Switzerland.
Angew Chem Int Ed Engl. 2018 May 4;57(19):5408-5412. doi: 10.1002/anie.201801452. Epub 2018 Mar 20.
Halogen- and chalcogen-based σ-hole interactions have recently received increased interest in non-covalent organocatalysis. However, the closely related pnictogen bonds have been neglected. In this study, we introduce conceptually simple, neutral, and monodentate pnictogen-bonding catalysts. Solution and in silico binding studies, together with high catalytic activity in chloride abstraction reactions, yield compelling evidence for operational pnictogen bonds. The depth of the σ holes is easily varied with different substituents. Comparison with homologous halogen- and chalcogen-bonding catalysts shows an increase in activity from main group VII to V and from row 3 to 5 in the periodic table. Pnictogen bonds from antimony thus emerged as by far the best among the elements covered, a finding that provides most intriguing perspectives for future applications in catalysis and beyond.
基于卤素和硫族元素的σ-空穴相互作用最近在非共价有机催化中受到越来越多的关注。然而，与之密切相关的氮族元素键却被忽视了。在本研究中，我们引入了概念上简单、中性且单齿的氮族元素键合催化剂。溶液和计算机模拟结合研究，以及在氯化物提取反应中的高催化活性，为氮族元素键的实际作用提供了有力证据。σ-空穴的深度很容易随不同取代基而变化。与同源的卤素和硫族元素键合催化剂相比，活性从元素周期表中的第VII主族增加到第V主族，从第3周期增加到第5周期。因此，锑形成的氮族元素键在涵盖的元素中是迄今为止最好的，这一发现为催化及其他领域的未来应用提供了最引人入胜的前景。
