A sulfur-mediated umpolung strategy employing N-thiosuccinimides and (EtO)2P(O)SH has been developed to synthesize unsymmetrical organophosphorus disulfides (P(O)-S-S motif). A pronucleophile (EtO)2P(O)SH, Bronsted acid and phosphorothioate nucleophile, converts N-thiosuccinimides into unsymmetrical...