School of Chemistry and Chemical Engineering, Key Laboratory of the Colloid and Interface Chemistry, Ministry of Education, Shandong University, Jinan, 250100, China.
College of Chemistry and Chemical Engineering, Key Laboratory of Special Function Materials and Structure Design of Ministry of Education, Lanzhou University, Lanzhou, 730000, China.
Angew Chem Int Ed Engl. 2021 Apr 19;60(17):9395-9400. doi: 10.1002/anie.202101140. Epub 2021 Mar 11.
While the presence of sulfur⋅⋅⋅π bonding interaction is a general phenomenon in the biological systems, the exploitation of this noncovalent force in a chemical process yet remains elusive. Herein, we describe the concept of chalcogen⋅⋅⋅π bonding catalysis that activates molecules of π systems through the interaction between chalcogen and π-electron cloud. The proof-of-concept studies using a vinylindole-based Diels-Alder benchmark reaction demonstrate that S⋅⋅⋅π and Se⋅⋅⋅π bonding interaction can drive the cycloaddition reaction efficiently. Experimental results suggest that a simultaneously double Se⋅⋅⋅π bonding interaction directs the stereoselectivity in this cycloaddition process.
虽然硫······π键相互作用在生物体系中是一种普遍现象，但在化学过程中利用这种非共价力仍然难以捉摸。在此，我们描述了硫属······π键催化的概念，该概念通过硫属元素与π-电子云之间的相互作用来激活π体系的分子。使用基于乙烯基吲哚的 Diels-Alder 基准反应的概念验证研究表明，S······π 和 Se······π 键相互作用可以有效地驱动环加成反应。实验结果表明，同时的双重 Se······π 键相互作用指导了这个环加成过程中的立体选择性。
