sulfonic acid (TfOH) in hexafluoroisopropanol (HFIP) promotes a Brønsted acid-assisted Brønsted acid catalysis strategy for arylating epoxides and a range of alcohols (Scheme 1a). Our lab recently reported conditions for setting quaternary carbon centers in site-selective Friedel-Crafts reactions using unactivated tertiary alcohols and catalytic combinations of FeX3/HX (Scheme 1b). Aside from a few isolated examples with cycloalkanols, the Cook group found that a mixture of FeCl3/AgSbF6 is effective at arylating unactivated secondary alcohols, albeit with little site-selectivity (Scheme 1c). less hindered ortho-site (Scheme 2a). We further demonstrate derivatization of the alkylated phenolic compound (3ah) with a Conditions: reactions performed on 0.1 mmol scale, phenol 1a (1 equiv), alcohol 2a (5 equiv), 18 h. b Determined by NMR analysis of the crude reaction mixture using 1,3,5-trimethoxybenzene as internal standard. c With 3 equiv 2a. d Isolated yield.