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

The first C-SCF₃ /SeCF₃ cross-coupling reactions using gold redox catalysis [(MeDalphos)AuCl], AgSCF₃ or Me₄ NSeCF₃ , 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.