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.