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The synthesis of advanced substituted 3-pentafluorosulfanylphenol/anisole was accomplished starting from the easy to access and commercially available 3-pentafluorosulfanylphenol. These products bear diverse substitutions such as ester, aldehyde, halogens, alcohol, nitrile and carboxylic acid and could be in the future used as high-value building blocks for the synthesis of various scaffolds. For our part, this intermediate had been used to synthesize a library of 2-arylindadiones substituted by a pentafluorosulfanyl group.