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

5,8-Dimethyl-1,12-dimethylene-2,11-dithia[3.3]cyclophane 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 add to the triple bonds of disubstituted benzenes. Experimental observations allowed mechanistic and stereochemical insights into the key step of the synthetic pathway, and NMR experiments were diagnostic for the structure assignments of the cage-like compounds. The stereochemical characteristics of the new dithiacyclophane S,S-dioxides synthesized may be applicable in the field of organocatalysis.