Synthesis of Enantiomerically Pure Bis‐Sulfinyl Substituted Phenylene Ethynylenes

The stereoselective and efficient monoaddition of transient [(1S,2R,4R)-2-hydroxy-7,7-dimethylbicyclo[2.2.1]hept-1-yl]methanesulfenic (=(1S)-isoborneol-10-sulfenic) acid to isomeric diethynylbenzenes affords {1-[(1S)-isoborneol-10-sulfinyl]ethenyl}ethynylbenzenes. Their enantiomerically pure (RS)-epimers are involved in a Cu-free Sonogashira coupling with 1,4-diiodo-2,5-dimethoxybenzene to give C2-symmetric bis-sulfinyl phenylene ethynylenes, stimulating prototypes of new sulfurated chiral architectures that can find application as chelating agents.