Anion–π Catalysis Enabled by the Mechanical Bond

We report a series of rotaxane‐based anion–π catalysts in which the mechanical bond between a bipyridine macrocycle and an axle containing an NDI unit is intrinsic to the activity observed, including a [3]rotaxane that catalyses an otherwise disfavoured Michael addition in >60 fold selectivity ov...

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Detalles Bibliográficos
Autores principales: Maynard, John R. J., Galmés, Bartomeu, Stergiou, Athanasios D., Symes, Mark D., Frontera, Antonio, Goldup, Stephen M.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2022
Materias:
Research Articles
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9303940/
https://www.ncbi.nlm.nih.gov/pubmed/35040543
http://dx.doi.org/10.1002/anie.202115961
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author Maynard, John R. J.
Galmés, Bartomeu
Stergiou, Athanasios D.
Symes, Mark D.
Frontera, Antonio
Goldup, Stephen M.
author_facet Maynard, John R. J.
Galmés, Bartomeu
Stergiou, Athanasios D.
Symes, Mark D.
Frontera, Antonio
Goldup, Stephen M.
author_sort Maynard, John R. J.
collection PubMed
description We report a series of rotaxane‐based anion–π catalysts in which the mechanical bond between a bipyridine macrocycle and an axle containing an NDI unit is intrinsic to the activity observed, including a [3]rotaxane that catalyses an otherwise disfavoured Michael addition in >60 fold selectivity over a competing decarboxylation pathway that dominates under Brønsted base conditions. The results are rationalized by detailed experimental investigations, electrochemical and computational analysis.
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spelling pubmed-93039402022-07-28 Anion–π Catalysis Enabled by the Mechanical Bond Maynard, John R. J. Galmés, Bartomeu Stergiou, Athanasios D. Symes, Mark D. Frontera, Antonio Goldup, Stephen M. Angew Chem Int Ed Engl Research Articles We report a series of rotaxane‐based anion–π catalysts in which the mechanical bond between a bipyridine macrocycle and an axle containing an NDI unit is intrinsic to the activity observed, including a [3]rotaxane that catalyses an otherwise disfavoured Michael addition in >60 fold selectivity over a competing decarboxylation pathway that dominates under Brønsted base conditions. The results are rationalized by detailed experimental investigations, electrochemical and computational analysis. John Wiley and Sons Inc. 2022-02-03 2022-03-14 /pmc/articles/PMC9303940/ /pubmed/35040543 http://dx.doi.org/10.1002/anie.202115961 Text en © 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH https://creativecommons.org/licenses/by/4.0/This is an open access article under the terms of the http://creativecommons.org/licenses/by/4.0/ (https://creativecommons.org/licenses/by/4.0/) License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.
spellingShingle Research Articles
Maynard, John R. J.
Galmés, Bartomeu
Stergiou, Athanasios D.
Symes, Mark D.
Frontera, Antonio
Goldup, Stephen M.
Anion–π Catalysis Enabled by the Mechanical Bond
title Anion–π Catalysis Enabled by the Mechanical Bond
title_full Anion–π Catalysis Enabled by the Mechanical Bond
title_fullStr Anion–π Catalysis Enabled by the Mechanical Bond
title_full_unstemmed Anion–π Catalysis Enabled by the Mechanical Bond
title_short Anion–π Catalysis Enabled by the Mechanical Bond
title_sort anion–π catalysis enabled by the mechanical bond
topic Research Articles
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9303940/
https://www.ncbi.nlm.nih.gov/pubmed/35040543
http://dx.doi.org/10.1002/anie.202115961
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AT symesmarkd anionpcatalysisenabledbythemechanicalbond
AT fronteraantonio anionpcatalysisenabledbythemechanicalbond
AT goldupstephenm anionpcatalysisenabledbythemechanicalbond

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