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Published on: August 12, 2019
Unclicking the Click: Metal-Assisted Mechanochemical Cycloreversion of Triazoles Is Possible
Martin Krupička1,2, Przemyslaw Dopieralski1,3, Dominik Marx1
1Lehrstuhl für Theoretische Chemie, Ruhr-Universität Bochum, 44780, Bochum, Germany.
Abstract:
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.
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