Trifluoromethylthiolation of Diazo Compounds through Copper Carbene Migratory Insertion

A strategy to introduce the SCF 3 group through the Cu I ‐promoted reaction of diazo compounds with the nucleophilic AgSCF 3 trifluoromethylthiolation reagent was developed. Various diazo compounds were smoothly converted under mild conditions to form the C(sp 3 )–SCF 3 bond. Mechanistically, migratory insertion of SCF 3 ‐bearing Cu carbene intermediates is involved in this transformation.