Arylation of Axially Chiral Phosphorothioate Salts by Dinuclear PdI Catalysis.

S-aryl phosphorothioates are privileged motifs in pharmaceuticals, agrochemicals, and catalysts; yet, the challenge of devising a straightforward synthetic route to enantioenriched S-aryl phosphorothioates has remained unsolved to date. We demonstrate herein the first direct C-SP(=O)(OR')(OR'') coupling of diverse and chiral phosphorothioate salts with aryl iodides, enabled by an air- and moisture-stable PdI dimer. Our mechanistic and computational data suggest distinct dinuclear PdI catalysis to be operative, which allows for operationally simple couplings with broad scope and full retention of stereochemistry.