Triphenylphosphine-Mediated Deoxygenative Reduction of CF3 SO2 Na and Its Application for Trifluoromethylthiolation of Aryl Iodides.

We report herein a practical method for taming Langlois' reagent CF3 SO2 Na to generate CuSCF3 by a triphenylphospine-mediated deoxygenative reduction process. This chemistry highlights a novel utilization of the inherent CF3 S skeleton of Langlois' reagent as a CF3 S feedstock under mild conditions. The CuSCF3 intermediate generated by this protocol can react with a wide array of supporting ligands to furnish several air-stable [LCu(SCF3 )] complexes as valuable trifluoromethylthiolating agents. In addition, the CuSCF3 intermediate can be directly employed for the trifluoromethylthiolation of (hetero)aryl iodides with operational simplicity and atomic efficiency.