Nickel and Palladium Catalyzed C−H Trifluoromethylation using Trifluoromethyliodide: Investigations into New Reactivity

Abstract Due to the prevalence of trifluoromethyl group (CF 3 ) in high‐value organic compounds, there is a constant demand for more selective, efficient and economical trifluoromethylation strategies. In this report we present detailed experimental computational investigations into use cheap atom‐economical CF I transition metal catalyzed trifluoromethylation. The mechanistic insight gained allowed novel C−H processes be developed, using both palladium nickel catalysis. reported methodology remarkably selective trifluoromethylation, with substituents such as amino, nitro, bromo aldehydes tolerated. Our studies suggest that radical species are not involved, key activation step facilitated by an unusual difluorocarbene intermediate. Importantly, arylCF formation occurs through unique 2 ‐F based reductive elimination, likely from Pd (II) /Ni but potentially oxidatively‐induced elimination (IV) . This first example nickel‐mediated where can occur catalytic manner.