Cu(III) Trifluoromethyl Complexes with 1,3‐Diketonate Ligands and Their Versatile Reactivity in C−H Trifluoromethylation

Abstract High‐valent Cu(III) trifluoromethyl complexes with 1,3‐diketonates as bidentate oxygen donor ligands LCu(III)(CF 3 ) 2 were prepared for the first time and fully characterized, including by X‐ray crystallography. These complexes are bench stable and soluble in most organic solvents. Promising reactivity of Cu(III) trifluoromethyl diketonates in radical and radical‐polar crossover trifluoromethylation reactions was demonstrated. Direct C−H trifluoromethylation of electron‐rich arenes and indoles using Cu(III) trifluoromethyl diketonates under blue light irradiation is described. Azolo‐ and oxy‐trifluoromethylation of terminal alkynes and S‐trifluoromethylation of aromatic thiol can be achieved using LCu(III)(CF 3 ) 2 in mild conditions.