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Anion-π Catalysis Enabled by the Mechanical Bond

23 November 2021, Version 1
Working Paper
This content is a preprint and has not undergone peer review at the time of posting.

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.

Keywords

anion–π catalysis
rotaxanes
mechanical bonds
DFT calculation

Supplementary materials

Title
Description
Actions
Title
Cif for rotaxane 4a
Description
xray diffraction data for rotaxane 4a
Actions
Title
Electronic supporting information for Maynard Anion Pi Rotaxane
Description
Full characterisation data, details of molecular modelling and electrochemistry, additional discussion
Actions
Title
Cif for rotaxane 4aH+
Description
xray diffraction data for rotaxane 4aH+
Actions

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Version History

Nov 23, 2021 Version 1

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The content is available under CC BY 4.0 [opens in a new tab]

DOI

10.26434/chemrxiv-2021-r591n
D O I: 10.26434/chemrxiv-2021-r591n [opens in a new tab]

Funding

European Research Council
724987
Royal Society
RSWF\FT\180010
MICIU/AEI of Spain
PID2020-115637GB-I00 FEDER
Royal Society
UF150104

Author’s competing interest statement

The author(s) have declared they have no conflict of interest with regard to this content

Ethics

The author(s) declare that they have sought and gained approval from the relevant ethics committee/IRB for this research and its publication.

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