“…[9] In the above studies, as well as in most of related developments and applications of iodine(III)-based compounds, the benziodoxol(on)e reagents have primarily been utilized as electrophilic group transfer agents in a general sense, with the iodine(III) center eventually converting to the stable iodine(I) oxidation state. However, drawing from our recent discovery of carboiodanation of arynes with alkynyl-, alkenyl-, and (hetero)arylbenziodoxoles (Scheme 1b), [10,11] where the organic ligands are transferred nucleophilically while maintaining the iodine(III) oxidation state, we posited that inherently electronrich heteroatom-containing benziodoxoles could also serve as nucleophilic group transfer agents in the reaction with arynes. Herein, we report the synthesis of amino-and alkoxybenziodoxoles (amino-and alkoxy-BXs) that feature the bis(trifluoromethyl)benzyl alcohol skeleton and their use in amino-and alkoxyiodanation of arynes (Scheme 1c).…”