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

High-valent Cu(III) trifluoromethyl complexes with 1,3-diketonates as bidentate oxygen donor ligands LCu(III)(CF3)(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)(CF3)(2) in mild conditions.

Automated summary

High-valent Cu(III) trifluoromethyl complexes with 1,3-diketonates as bidentate oxygen donor ligands LCu(III)(CF3)(2) were synthesized and characterized. They exhibit bench stability and solubility in organic solvents. The reactivity of Cu(III) trifluoromethyl diketonates in radical and radical-polar crossover trifluoromethylation reactions was demonstrated, along with the direct C-H trifluoromethylation of electron-rich arenes and indoles and the azolo- and oxy-trifluoromethylation of terminal alkynes and aromatic thiol using LCu(III)(CF3)(2) under mild conditions.