Synthesis and Applications of Sulfur-Containing Macrocycles

Abstract

In recent years, methylene-bridged macrocycles have emerged as versatile scaffolds in supramolecular architecture, owing to their intrinsically defined cavities, facile functionalization, and sophisticated host-guest recognition motifs. The strategic engineering of macrocyclic frameworks with tailored functionalities remains a cornerstone of synthetic supramolecular chemistry. In particular, the precise incorporation of heteroatoms-such as sulfur, nitrogen, or oxygen-into these backbones effectively modulates their cavity microenvironments, conformational landscapes, and electronic states. Such modifications impart unique physicochemical properties and binding affinities that transcend those of traditional hydrocarbon macrocycles. This review focuses on the burgeoning field of sulfur-containing macrocycles, providing a systematic overview of their rational design principles, atom-economic synthesis, and multifaceted applications in recognition, separation, and materials science. Finally, we delineate the remaining challenges and future prospects to provide a comprehensive roadmap for the development of the next generation of functional macrocyclic hosts.

Keywords: fragment coupling; macrocycle‐to‐macrocycle interconversion; one‐pot method; post‐synthetic modifications; sulfur‐containing macrocycles.