Unsymmetrical Disulfides Synthesis via Sulfenium Ion

An umpolung approach for the synthesis of unsymmetrical disulfides via sulfenium ion is reported. In situ generated electrophilic sulfenium ion from electron‐rich thiols reacted with second thiols to yield unsymmetrical disulfides. Using an iodine catalyst and 4‐dimethylaminopyridine (DMAP)/water as promoter, the target syntheses were achieved in one pot under aerobic condition. Dual promoters! Using an iodine catalyst and 4‐dimethylaminopyridine (DMAP)/water as promoter, selective syntheses of unsymmetrical disulfides were achieved in one pot under aerobic conditions.