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
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author Modicom, Florian
Jamieson, Ellen M. G.
Rochette, Elise
Goldup, Stephen M.
author_facet Modicom, Florian
Jamieson, Ellen M. G.
Rochette, Elise
Goldup, Stephen M.
author_sort Modicom, Florian
collection PubMed
description 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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spelling pubmed-65899162019-07-08 Chemical Consequences of the Mechanical Bond: A Tandem Active Template‐Rearrangement Reaction Modicom, Florian Jamieson, Ellen M. G. Rochette, Elise Goldup, Stephen M. Angew Chem Int Ed Engl Communications 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. John Wiley and Sons Inc. 2019-02-14 2019-03-18 /pmc/articles/PMC6589916/ /pubmed/30600892 http://dx.doi.org/10.1002/anie.201813950 Text en © 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the http://creativecommons.org/licenses/by/4.0/ License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.
spellingShingle Communications
Modicom, Florian
Jamieson, Ellen M. G.
Rochette, Elise
Goldup, Stephen M.
Chemical Consequences of the Mechanical Bond: A Tandem Active Template‐Rearrangement Reaction
title Chemical Consequences of the Mechanical Bond: A Tandem Active Template‐Rearrangement Reaction
title_full Chemical Consequences of the Mechanical Bond: A Tandem Active Template‐Rearrangement Reaction
title_fullStr Chemical Consequences of the Mechanical Bond: A Tandem Active Template‐Rearrangement Reaction
title_full_unstemmed Chemical Consequences of the Mechanical Bond: A Tandem Active Template‐Rearrangement Reaction
title_short Chemical Consequences of the Mechanical Bond: A Tandem Active Template‐Rearrangement Reaction
title_sort chemical consequences of the mechanical bond: a tandem active template‐rearrangement reaction
topic Communications
url 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
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