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.