The diarylation of N-and O-nucleophiles was proposed to proceed via initial SNAr to form a Meisenheimer complex followed by intramolecular aryl transfer. A related mechanism can be proposed for the S-diarylation, where the S-nucleophile forms the SNAr product A, followed by hydrolysis of the xanthogenate to B and carbonothioate derivative C, followed by intramolecular aryl transfer to yield diarylated product 3 (Scheme 4A). Alternatively, the aryl transfer could proceed before hydrolysis via intermediate D. The SNAr step could proceed via a stepwise or concerted mechanism, as previously reported in S-arylation. Cleavage of the xanthogenate intermediate via Chugaev elimination is unlikely, due to the low reaction temperature. The mechanism was investigated by the isolation of key intermediates. This was carried out by shortening the reaction time and adding diethyl ether to precipitate out key intermediates. To our satisfaction, SNAr product 6a could be isolated as a lightyellow solid in 69% yield (Scheme 4B). However, 6a was unstable in the NMR solvent and gradually transformed to product 3b when subjected to the standard conditions. Then 6a was transformed to transformed to the methylated sulfide 6b in 83% isolated yield, which confirms the structure of 6a. Kinetic experiments suggest fast formation of the intermediate and gradual transformation to the product. At the end of the reaction carbonothioate derivative 7a was detected in crude 1 H-NMR and HRMS, which suggests that hydrolysis of the xanthogenate derivative takes place. Br 5j 89%, >20:1 5i 69%, 20:1 5g 89%, >20:1 5f 79%, 9:1 5 (E:Z ratio below) H 5a 80%, >20:1 Me 5b 72%, >20:1 Cl 5c 86%, >20:1 Ph 5d 73%, 5:1 OMe 5e 48%, 9:1 S I NO 2 D D 5k 79%, >20:1 2c (2 equiv)