Premium
Unclicking the Click: Metal‐Assisted Mechanochemical Cycloreversion of Triazoles Is Possible
Author(s) -
Krupička Martin,
Dopieralski Przemyslaw,
Marx Dominik
Publication year - 2017
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201612507
Subject(s) - click chemistry , chemistry , triazole , catalysis , metal , nanotechnology , combinatorial chemistry , photochemistry , materials science , organic chemistry
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 Cu I 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 Ru II catalysis.