Unusual Effect of Impurities on the Spectral Characterization of 1,2,3-Triazoles Synthesized by the Cu-Catalyzed Azide–Alkyne Click Reaction
The analysis of products synthesized by Cu-catalyzed click reactions can be complicated due to the presence of metal impurities in isolated substances, which may "selectively" distort some signals in NMR spectra. Such a pronounced impurity effect was found in both 1H and 13C NMR spectra for a number of 1,4-substituted 1,2,3-triazoles. Recording of the full undistorted spectra is possible with additional product treatment, with more thorough purification, or by recording the spectra at low temperatures. The reasons for the distortion and disappearance of signals have been thoroughly studied; it was shown that impurities of paramagnetic metal ions in small amounts lead to this effect. Here, we want to deliver a warning message to the community: when all NMR signals in a spectrum are distorted, this situation is easy to detect. However, if only a few signals are "selectively" removed by impurities and the rest of the spectrum appears normal, this situation is much harder to notice. Therefore, incorrect conclusions about chemical structure may be obtained. Here, we demonstrated the example of Cu2+ ions, but one may anticipate a similar effect for other paramagnetic metal contaminants if the organic molecule has a functional group capable of coordination (heteroatom or a multiple bond).
Reference: J. Org. Chem., 2021, ASAP
