Trifluoromethylthiolation of Diazo Compounds through Copper Carbene Migratory Insertion

A strategy to introduce the SCF3 group through the CuI‐promoted reaction of diazo compounds with the nucleophilic AgSCF3 trifluoromethylthiolation reagent was developed. Various diazo compounds were smoothly converted under mild conditions to form the C(sp3)–SCF3 bond. Mechanistically, migratory insertion of SCF3‐bearing Cu carbene intermediates is involved in this transformation. A strategy to introduce the SCF3 group through the CuI‐promoted reaction of diazo compounds with the nucleophilic AgSCF3 trifluoromethylthiolation reagent is developed. Various diazo compounds are smoothly converted under mild conditions to form the C(sp3)–SCF3 bond. Migratory insertion of SCF3‐bearing CuI carbene intermediates is proposed as the key step in this transformation.