Using exclusively Selectfluor ® throughout the following experiments we started further optimizations with o-iodophenol (3a, R = H, Table ) as the model substrate. Coupling with the aryne precursor 4a, subsequent oxidation for 24 h and cyclization with 4.0 equiv. BF3•OEt2 at room temperature yielded the desired iodaoxinium salt 1a in 35% yield (entry 1) as the triflate salt. When the cyclization step was performed at 0 °C the yield increased to 42% (entry 2). At -40 °C the desired product was obtained in 52% yield (entry 3). The use of AcOH as additive for the oxidation step resulted in a significantly diminished side product formation, most likely due to the formation of the more stable bisacetoxy I(III) derivate 6a (L = OAc). This finally resulted in an improved formation of 1a (62% yield, entry 4). A further significant improvement was achieved through addition of TfOH during the cyclization step which increased the yield of 1a to 78% (entry 5). Performing the cyclization at 0 °C resulted in a diminished yield (entry 6). Further replacement of BF3•OEt2 with TfOH further increased the yield of 1a to satisfying 81% (entry 7).