The rise of halogen bonding in (stereo)selective supramolecular catalysis

Since its emergence in the late 1970s, supramolecular chemistry has become a cornerstone of modern chemical science. Defined by the controlled assembly of molecular components through reversible interactions, it encompasses a wide spectrum of forces, among which halogen bonding (XB) has gained prominence as a versatile and directional interaction with unique applications in molecular design and catalysis. This review highlights catalytic systems in which halogen bonding functions either (i) as an activating interaction toward functional groups; (ii) as a promoter of halogen abstraction in organic substrates and metal complexes; or (iii) as a structural element directing the assembly of the catalyst framework. To maintain a focused and critical perspective, only catalytic systems employing 10 mol% of catalyst or less and demonstrating applicability to the synthesis of structurally diverse product arrays are discussed. The review is organized according to the role of the catalyst, providing a coherent framework for understanding how halogen bonding governs activation, selectivity, and molecular organization. Collectively, the studies discussed herein illustrate how halogen bonding has evolved from a supramolecular curiosity into a tool in catalysis, expanding both the conceptual and practical boundaries of modern supramolecular catalysis.