LAUSR

Cyclophanes are a venerable class of compounds that often display unusual properties due to their high strain and unusual conformations. The exploration of new, complex cyclophanes has sometimes encountered challenging stepwise syntheses that can be low yielding, require harsh reaction conditions, and/or involve arduous purification steps. Herein, we discuss our work using metalloid-directed self-assembly, which led to a serendipitous discovery that dynamic covalent chemistry featuring disulfide bonds could provide a new route to form cyclophanes in these systems. This resulted in a mild set of reaction methods using self-assembly, thiol oxidation, and sequential “kinetic capture” via sulfur extrusion to yield a series of discrete disulfide, thioether, and hydrocarbon macrocycles, and in some cases, cages. ‘Design of Experiments’ was then used to selectively synthesize targeted macrocycles and cages from these more complex mixtures.