Selective Ortho Thiolation Enabled by Tuning the Ancillary Ligand in Palladium/Norbornene Catalysis

Site-selective introduction of a sulfur group into aromatic compounds is essential and useful in organic, material, and pharmaceutical chemistry. A palladium/norbornene-catalyzed chemoselective ortho thiolation of aryl halides was reported. The selectivity of reductive elimination for C­(Ar)–SR bond formation was well controlled by tuning the ancillary ligand in the aryl-NBE palladacycle Pd­(IV) intermediate. The reaction showcased good substrate scope: both S-alkyl and S-aryl thiosulfonates were compatible.