GONZALEZ, J.P. ... et al., 2011. Synthesis of fluorinated fused benzofurans and benzothiophenes: smiles-type rearrangement and cyclisation of perfluoro(het)aryl ethers and sulfides. Organic and Biomolecular Chemistry, 9 (7), pp. 2294 - 2305.
Lithium–bromine exchange in 2-bromophenyl perfluoroaryl ethers or sulfides affords fused fluorinated benzofurans or benzothiophenes respectively by SNAr substitution of the adjacent fluorine in the perfluoroaryl substituent. The structures of the new compounds were confirmed by NMR spectroscopy and single crystal X-ray diffraction analysis. In the case of 2-bromophenyl tetrafluoropyrid-4-yl ether, lithiation promoted a Smiles-type rearrangement which led to formation of 4-(2-hydroxyphenyl)tetrafluoropyridine, for which the structure was confirmed by X-ray crystallography.