Copper‐Catalyzed Remote C(sp³)−H Trifluoromethylation of Carboxamides and Sulfonamides

Reported herein is an unprecedented protocol for trifluoromethylation of unactivated aliphatic C(sp³ )-H bonds. With Cu(OTf)₂ as the catalyst, the reaction of N-fluoro-substituted carboxamides (or sulfonamides) with Zn(CF₃ )₂ complexes provides the corresponding δ-trifluoromethylated carboxamides (or sulfonamides) in satisfactory yields under mild reaction conditions. A radical mechanism involving 1,5-hydrogen atom transfer of N-radicals followed by CF₃ -transfer from CuII -CF₃ complexes to the thus formed alkyl radicals is proposed.