Transition-metal-free regioselecitive C-H arylation of 2-naphthols with diaryliodonium salts has been developed. The reaction proceeds under very simple experimental conditions and affords a range of products with various substitution patterns. The method allows for the incorporation of electron-deficient aryls, which complements well currently existing metal-free aryl-aryl cross-couplings of phenols that have been so far restricted to the introduction of electron-rich aryl moieties. The mechanism of the reaction was studied by means of DFT calculations, demonstrating that the C-C bond formation occurs via a dearomatization of 2-naphthol substrate, followed by a subsequent rearomatization by tautomerization. The computations show that the use of a low polarity solvent and an insoluble inorganic base is key to securing the high selectivity of the C-C coupling over a competing C-O arylation pathway, by preventing the incipient deprotonation of 2-naphthol.
Keywords: C−H functionalization; cross-coupling; density functional calculations; diaryliodonium salts; naphthols.
© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.