Anion-π catalysis enabled by the mechanical bond
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 over a competing decarboxylation pathway that dominates under Brønsted base conditions. The results are rationalized by detailed experimental investigations, electrochemical and computational analysis.
Anion-pi Catalysis, DFT Calculations, Mechanical Bonds, Rotaxanes, Supramolecular Chemistry, Anion–π Catalysis
Goldup, Stephen
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Maynard, John
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Galmés, Bartomeu
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Stergiou, Athanasios
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Symes, Mark
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Frontera, Antonio
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14 March 2022
Goldup, Stephen
0a93eedd-98bb-42c1-a963-e2815665e937
Maynard, John
4e09e766-1294-4056-8bff-4277874f0495
Galmés, Bartomeu
ae4826f4-cff0-4e07-af27-fa9b1274bf6b
Stergiou, Athanasios
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Symes, Mark
b8ec5ec5-0b20-44ae-87c8-3b4e9e1fa80e
Frontera, Antonio
304cf852-ac79-4d19-9ee5-e169bf5957bd
Goldup, Stephen, Maynard, John, Galmés, Bartomeu, Stergiou, Athanasios, Symes, Mark and Frontera, Antonio
(2022)
Anion-π catalysis enabled by the mechanical bond.
Angewandte Chemie International Edition, 61 (12), [e202115961].
(doi:10.1002/anie.202115961).
Abstract
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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e-pub ahead of print date: 18 January 2022
Published date: 14 March 2022
Additional Information:
Funding Information:
The authors thank Graham Tizzard of the EPSRC National Crystallography Service for assistance finalising the SCXRD analysis. S.M.G. thanks the European Research Council (Consolidator Grant Agreement no. 724987) for funding and the Royal Society for a Wolfson Research Fellowship (RSWF\FT\180010). A.D.S. thanks the Royal Society for a PhD studentship award and M.D.S. thanks the Royal Society for a University Research Fellowship (150104). B.G. and A.F. thank the MICIU/AEI of Spain (project PID2020-115637GB-I00 FEDER funds) for funding.
Funding Information:
The authors thank Graham Tizzard of the EPSRC National Crystallography Service for assistance finalising the SCXRD analysis. S.M.G. thanks the European Research Council (Consolidator Grant Agreement no. 724987) for funding and the Royal Society for a Wolfson Research Fellowship (RSWF\FT\180010). A.D.S. thanks the Royal Society for a PhD studentship award and M.D.S. thanks the Royal Society for a University Research Fellowship (150104). B.G. and A.F. thank the MICIU/AEI of Spain (project PID2020‐115637GB‐I00 FEDER funds) for funding.
Publisher Copyright:
© 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.
Keywords:
Anion-pi Catalysis, DFT Calculations, Mechanical Bonds, Rotaxanes, Supramolecular Chemistry, Anion–π Catalysis
Identifiers
Local EPrints ID: 454745
URI: http://eprints.soton.ac.uk/id/eprint/454745
ISSN: 1433-7851
PURE UUID: 48fd3cf3-281b-47dc-b29f-1991c5488490
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Date deposited: 22 Feb 2022 17:39
Last modified: 05 Jun 2024 19:57
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Contributors
Author:
John Maynard
Author:
Bartomeu Galmés
Author:
Athanasios Stergiou
Author:
Mark Symes
Author:
Antonio Frontera
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