Chemical Consequences of the Mechanical Bond: A Tandem Active Template‐Rearrangement Reaction

We report the unexpected discovery of a tandem active template CuAAC‐rearrangement process, in which N(2) is extruded on the way to the 1,2,3‐triazole product to give instead acrylamide rotaxanes. Mechanistic investigations suggest this process is dictated by the mechanical bond, which stabilizes th...

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Detalles Bibliográficos
Autores principales: Modicom, Florian, Jamieson, Ellen M. G., Rochette, Elise, Goldup, Stephen M.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2019
Materias:
Communications
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6589916/
https://www.ncbi.nlm.nih.gov/pubmed/30600892
http://dx.doi.org/10.1002/anie.201813950
Descripción
Sumario:We report the unexpected discovery of a tandem active template CuAAC‐rearrangement process, in which N(2) is extruded on the way to the 1,2,3‐triazole product to give instead acrylamide rotaxanes. Mechanistic investigations suggest this process is dictated by the mechanical bond, which stabilizes the Cu(I)‐triazolide intermediate of the CuAAC reaction and diverts it down the rearrangement pathway; when no mechanical bond is formed, the CuAAC product is isolated.

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