After these promising results, we were eager to test the ENHIs in other group transfer reactions (Scheme 3). Reaction of ethyl 2-cyano-3-phenylpropanoate 7 (Scheme 3 -a) with the N-bound triazole 1c gave the alkynylated product 8 in a good yield of 71% which is a comparative reactivity to TIPS-EBX (6). The alkynylation of thiophenole 9 with 1,5,7triazabicyclo(4.4.0)dec-5-ene (TBD) to 10 gave only a low product formation of 26% and therefore a significant lower reactivity than TIPS-EBX (Scheme 3 -b). Waser and coworkers also observed a low reactivity of their N-heterocyclic iodanes in this reaction. Calculated MEP-maps of those iodanes reveal a lower electron density of the N-I-bond and assumes a decreased σ-hole compared to TIPS-EBX as a putative reason. Finally, the alkynylation of amines was tested using N-tosylaniline (11). Instead of an aniline alkynylation, N-alkynylation of the ENHI 1a,b was observed, giving N-alkynylated triazoles 12a and 12b in 47% and 41% (Scheme 3 -c). MS/MS experiments of 12a strongly indicated a selective alkynylation of the triazoles N2 (see ESI). Interestingly the absence of N-tosylaniline leads to only a low intramolecular conversion. Based on this observation, the direct thermolysis as another intramolecular transformation pathway was investigated. While using the pseudocyclic salts 1a and 1d the emerging TfOH leads to no product formation, the cyclic NHIs 2a and 2d gave the TIPS-acetylene triazole 14 in 49% (Scheme 3 -d) and benzimidazole 16 in 35% yield (Scheme 3 -f).