Abstract
The chemoselective reaction of the C- followed by the O-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 C2spCsp2<math> <mrow><msubsup><mtext>C</mtext> <mrow><mi>s</mi> <mi>p</mi></mrow> <mn>2</mn></msubsup> </mrow> </math> - C2spCsp2<math> <mrow><msubsup><mtext>C</mtext> <mrow><mi>s</mi> <mi>p</mi></mrow> <mn>2</mn></msubsup> </mrow> </math> /O- C2spCsp2<math> <mrow><msubsup><mtext>C</mtext> <mrow><mi>s</mi> <mi>p</mi></mrow> <mn>2</mn></msubsup> </mrow> </math> bond formation. The naphthyl radicals were generated in the reaction by the tetramethylpiperidinyl radical (TMP·) which resulted from the homolytic fragmentation of the precursor TMP2O. Experimental and DFT calculations provided a complete panorama of the reaction mechanism.