Chalcogen bond in organocatalysis: bonding characteristics, catalytic mechanisms, and catalyst design

Abstract

The chalcogen bond, as an important noncovalent interaction, has garnered significant attention in organocatalysis due to its environmentally friendly, low-cost, excellent catalytic performance, and mild reaction conditions. The chalcogen bond is an attractive interaction between an electrophilic region (namely σ-hole) of a chalcogen atom and a nucleophilic region in another or the same molecule. The chalcogen-based σ-hole interaction is the driving force for chalcogen bond catalysis, which has facilitated a range of organic reactions, providing a novel platform for addressing reactivity and selectivity in complex transformations. In this review, by integrating relevant experimental findings and our own theoretical studies, we focus on the application of chalcogen bonds in organocatalysis—covering aspects from bonding characteristics and catalytic mechanisms to catalyst design. In light of the types of chalcogen bond driving force, we present chalcogen⋯N bond catalysis, chalcogen⋯O bond catalysis, chalcogen⋯halogen bond catalysis, chalcogen⋯π bond catalysis, and cooperative catalysis of the other noncovalent interactions. In addition, we summarize some challenges and outlook, and hope to stimulate further exploration of chalcogen bonds in organocatalysis.