An Efficient Route to Symmetrical and Unsymmetrical Disulfide, Thioether, and Hydrocarbon Cyclophanes

The union of metal‐directed self‐assembly, dynamic covalent chemistry, and sorting gives rise to 3 new unsymmetrical tetrameric disulfide macrocycles. Stepwise sulfur extrusion from the self‐assembled disulfides to, first, thioethers, and then to hydrocarbons by photochemically promoted routes, gives rise to a collection of 7 new thioether and hydrocarbon cyclophanes related to the venerable family of [ n ]paracyclophanes. These methods provide an efficient self‐assembly approach to the synthesis of hydrocarbon macrocycles (related to carbon “nanohoops”), a class of structures that are typically formed in lengthier, stepwise syntheses.