The Diaryliodonium(III) Salts Reaction With Free-Radicals Enables One-Pot Double Arylation of Naphthols.

The chemoselective reaction of the - followed by the centered naphthyl radicals with the more electron-deficient hypervalent bond of the diaryliodonium(III) salts is described. This discovered reactivity constitutes a new activation mode of the diaryliodonium(III) salts which enabled a one-pot doubly arylation of naphthols through the sequential - /O- bond formation. The naphthyl radicals were generated in the reaction by the tetramethylpiperidinyl radical (TMP·) which resulted from the homolytic fragmentation of the precursor TMPO. Experimental and DFT calculations provided a complete panorama of the reaction mechanism.