Catalysis with Pnictogen, Chalcogen, and Halogen Bonds.

Catalysis with Pnictogen, Chalcogen, and Halogen Bonds.
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DOI:
10.1002/anie.201801452
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发表时间:
2018-05-04
期刊:
Angewandte Chemie (International ed. in English)
影响因子:
--
通讯作者:
Matile S
Matile S
中科院分区:
其他
文献类型:
--
作者:
Benz S;Poblador-Bahamonde AI;Low-Ders N;Matile S

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基于卤素和硫族的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,密切相关的pNictogen键被忽略了。在本研究中,我们介绍了概念上简单的、中性的和单齿的烟原键合催化剂。溶液和 的硅结合研究,再加上氯提取反应中的高催化活性,为操作pNictogen键提供了令人信服的证据。σ 空穴的深度很容易随取代基的不同而变化。与同系物的卤素和硫族键合催化剂相比,活性从元素周期表中主族 VII到V和从 3到5都有所提高。因此,来自锑的PNictogen键成为所涉及的元素中最好的,这一发现为未来在催化和其他领域的应用提供了最耐人寻味的前景。
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.
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