Stereoselective Synthesis of Dithia[3.3]cyclophaneS,S′-Dioxides with Planar and Central Chirality

5,8-Dimethyl-1,12-dimethylene-2,11-dithia[3.3]cyclophanes 2,11-dioxides with planar and central chirality were synthesized in high yields, starting from 2,5-dimethyl-1,4-benzenedimethanethiol, through the formation of suitable transient sulfenic functions that added to the triple bonds of bis-substituted benzenes. Some experimental observations allowed a mechanistic and stereochemical entry into the key step of the synthetic pathway and NMR spectra were diagnostic for the structure assignments of such cage-like compounds. The stereochemical characteristics of dithiacyclophanes S,S-dioxides are spendable in the organocatalysis field.