4 years ago

Unclicking the Click: Metal-Assisted Mechanochemical Cycloreversion of Triazoles is Possible

Unclicking the Click: Metal-Assisted Mechanochemical Cycloreversion of Triazoles is Possible
Martin Krupička, Dominik Marx, Przemyslaw Dopieralski
The mechanochemical cycloreversion of 1,2,3-triazole compounds, which serve as unusually stable building blocks in materials and biomolecular chemistry as a result of mild “click chemistry”, remains puzzling. We show that the hitherto discussed straight-forward retro-click mechanism of the 1,4-disubstituted isomer, even if CuI catalyzed, can be ruled out in view of more favorable activation free energies of destructive pathways. In stark contrast, the 1,5-regioiomer can undergo cycloreversion under rather mild mechanochemical conditions owing to its favorable response to the external force in conjunction with standard RuII catalysis. Mechanochemical unclicking reactions of 1,2,3-triazoles have been a topic of controversy. Based on isotensional quantum-chemical calculations, it is shown that their 1,5-regioisomers easily undergo cycloreversion reactions under standard sonication conditions if they are RuII catalyzed.

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/anie.201612507

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