Anion–π catalysis enabled by the mechanical bond**

John R.J. Maynard; Bartomeu Galmés; Athanasios D. Stergiou; Mark D. Symes; Antonio Frontera; Stephen M. Goldup

doi:10.1002/anie.202115961

Anion–π catalysis enabled by the mechanical bond**

John R.J. Maynard, Bartomeu Galmés, Athanasios D. Stergiou, Mark D. Symes, Antonio Frontera^*, Stephen M. Goldup^*

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

4 Citations (Scopus)

9 Downloads (Pure)

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.

Original language	English
Article number	e202115961
Number of pages	8
Journal	Angewandte Chemie - International Edition
Volume	61
Issue number	12
Early online date	18 Jan 2022
DOIs	https://doi.org/10.1002/anie.202115961
Publication status	Published - 14 Mar 2022

Bibliographical note

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–π Catalysis
DFT Calculations
Mechanical Bonds
Rotaxanes
Supramolecular Chemistry

ASJC Scopus subject areas

Catalysis
General Chemistry

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MaynardJ2022AnionFinal published version, 1.84 MBLicence: Creative Commons: Attribution (CC BY)

Cite this

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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 Br{\o}nsted base conditions. The results are rationalized by detailed experimental investigations, electrochemical and computational analysis.",

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note = "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: {\textcopyright} 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.",

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AU - Frontera, Antonio

AU - Goldup, Stephen M.

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Anion–π catalysis enabled by the mechanical bond**

Abstract

Bibliographical note

Keywords

ASJC Scopus subject areas

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