Metal‐free arylation of thiols with diaryliodonium salts has been developed. The application of a strong organic base enables the C−S bond formation under mild and experimentally simple conditions. The method allows for the synthesis of aryl sulfides containing a broad range of aryl groups from an array of thiols, including aryl, heteroaryl, and alkyl ones. The mechanism of the reaction was studied by DFT calculations, demonstrating that it proceeds via the inner sphere pathway involving formation of an Ar2I(SR) intermediate, followed by reductive elimination.

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We developed a direct metal-free S-arylation of phosphorothioate diesters using diaryliodonium salts. The method allows for the preparation under simple conditions of a broad range of S-aryl phosphorothioates, including complex molecules (e.g., dinucleotide or TADDOL derivatives), as well as other related organophosphorus compounds arylated at a chalcogen. The reaction proceeds with a full retention of the stereogenic center at the phosphorus atom, opening convenient access to P-chiral products. The mechanism of the reaction was established using DFT calculations.

Metal-free arylation of thiols with diaryliodonium salts has been developed. The application of a strong organic base ena-bles the C–S bond formation under mild and experimentally simple conditions. The method allows for the synthesis of aryl sulfides containing a broad range of aryl groups from an array of thiols, including aryl, heteroaryl, and alkyl ones. The mechanism of the reaction was studied by DFT calculations, demonstrating that is follows the inner sphere pathway involv-ing the incipient formation of Ar2I(SR) intermediate, followed by the reductive elimination.

We developed a direct metal-free S-arylation of phosphorothioate diesters using diaryliodonium salts. The meth-od allows for the preparation under simple conditions of a broad range of S-aryl phosphorothioates, including complex molecules (e.g., dinucleotide- or TADDOL-derivatives), as well as other related organophosphorus compounds arylated at chalcogen. The reaction proceeds with a full retention of the stereogenic center at phos-phorus atom, opening convenient access to P-chiral products. The mechanism of the reaction was established using DFT calculations.