Arylation of Axially Chiral Phosphorothioate Salts by Dinuclear Pd I 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 Pd I dimer. Our mechanistic and computational data suggest distinct dinuclear Pd I catalysis to be operative, which allows for operationally simple couplings with broad scope and full retention of stereochemistry.