Gold (I/III)‐Catalyzed Trifluoromethylthiolation and Trifluoromethylselenolation of Organohalides

Abstract The first C−SCF 3 /SeCF 3 cross‐coupling reactions using gold redox catalysis [(MeDalphos)AuCl], AgSCF 3 or Me 4 NSeCF 3 , and organohalides as substrates are reported. The new methodology enables a one‐stop shop synthesis of aryl/alkenyl/alkynyl trifluoromethylthio‐ and selenoethers with a broad substrate scope (>60 examples with up to 97 % isolated yield). The method is scalable, and its robustness is evidenced by the late‐stage functionalization of various bioactive molecules, which makes this reaction an attractive alternative in the synthesis of trifluoromethylthio‐ and selenoethers for pharmaceutical and agrochemical research and development.