Metal‐Free and Thiol‐Free Approach to Diverse Thiacyclophanes

Here, we report various thiacyclophane derivatives starting with arylmethyl bromides and potassium thioacetate. We conducted a controlled synthesis of thiacyclophanes dimer, trimer, and tetramer by changing the concentration of reactants. The reaction conditions were optimized to improve the selectivity. All the reactions were performed in low dilution without using the high dilution technique, the only known direct synthetic method for these thiacyclophanes. The structures of various thiacyclophanes were confirmed by NMR studies and further supported by single‐crystal X‐ray diffraction data.