Haraldur Gunnar Gudmundsson

Herein, a convenient and operationally simple protocol for the ex‐situ generation of bis(trifluoromethyl)disulfide from the readily available and commercial Langlois reagent is reported. The one‐step synthesis of the toxic and volatile CF 3 SSCF 3 is performed in a two‐chamber reactor with simple PPh 3 and N ‐bromosuccinimide as the activator, allowing for the safe handling and tandem utilization in direct trifluoromethylthiolation reactions. The versatility of the ex‐situ generated CF 3 SSCF 3 is demonstrated in known electrophilic, nucleophilic, and a radical trifluoromethylthiolation reactions. Furthermore, the application of the CF 3 SSCF 3 in a copper‐catalyzed cross‐coupling with boronic acids is disclosed, showing good to excellent yields of trifluoromethyl‐substituted aryl products, including pharmaceutically relevant molecules.