improved yield of 5a after 1 h reaction time (70%, entry 4). Similar to the Me-triazoles, the cyclic iodane 2b gave a lower yield of 60% in direct comparison with the corresponding pseudocyclic salt 1b (entry 5). The same tendency was observed with the benzimidazoles (entries 6-7). This reactivity can be derived from the crystal structures. The shorter C-I-distance of the pseudocyclic derivative 1l (2.035 Å) compared with the cyclic iodane 2a (2.071 Å) indicates a stronger trans-effect of the pseudocyclic salts and therefore a higher reactivity in group transfer reactions. With the salts 1c, 1e and 1i a quantitative formation of the alkynyl product 5a was observed (entries 8-10) and showed a similar reactivity to TIPS-EBX (6) (entry 11). It is worth mentioning that in many reactions the iodoarenes 3 could be recovered in moderate to high yields. The Ph-alkynyl salt 1r was not reactive in this type of transfer reaction (entry 12). Using the methyl ester 4b with the triazole leads to a slightly lower yield of 5b (71%), while TIPS-EBX (6) again gave quantitative product formation (entries 13-14). [a] reaction time 18 h. [b] not clean after column chromatography. [c] without TBAF.