Chalcogen⋅⋅⋅π Bonding Catalysis

Abstract

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.