Catalysis enabled synthesis, structures, and reactivities of fluorinated S8-corona[n]arenes (n = 8–12)

Andrew. T. Turley; Magnus W. D. Hanson-Heine; Stephen. P. Argent; Yaoyang Hu; Thomas. A. Jones; Michael Fay; Simon Woodward

doi:10.1039/D2SC05348A

Catalysis enabled synthesis, structures, and reactivities of fluorinated S₈-corona[n]arenes (n = 8–12)†

Andrew. T. Turley,

*^a Magnus W. D. Hanson-Heine,

^b Stephen. P. Argent,

^b Yaoyang Hu,

^a Thomas. A. Jones,

^a Michael Fay

^c and Simon Woodward

*^a

Author affiliations

* Corresponding authors

^a GSK Carbon Neutral Laboratories for Sustainable Chemistry, University of Nottingham, Jubilee Campus, Nottingham NG7 2TU, UK
E-mail: andrew.turley@nottingham.ac.uk, simon.woodward@nottingham.ac.uk

^b School of Chemistry, University of Nottingham, University Park Campus, Nottingham NG7 2RD, UK

^c Nanoscale and Microscale Research Centre, University of Nottingham, University Park Campus, Cripps South Building, Nottingham, UK

Abstract

Previously inaccessible large S₈-corona[n]arene macrocycles (n = 8–12) with alternating aryl and 1,4-C₆F₄ subunits are easily prepared on up to gram scales, without the need for chromatography (up to 45% yield, 10 different examples) through new high acceleration S_NAr substitution protocols (catalytic NR₄F in pyridine, R = H, Me, Bu). Macrocycle size and functionality are tunable by precursor and catalyst selection. Equivalent simple NR₄F catalysis allows facile late-stage S_NAr difunctionalisation of the ring C₆F₄ units with thiols (8 derivatives, typically 95+% yields) providing two-step access to highly functionalised fluoromacrocycle libraries. Macrocycle host binding supports fluoroaryl catalytic activation through contact ion pair binding of NR₄F and solvent inclusion. In the solid-state, solvent inclusion also intimately controls macrocycle conformation and fluorine–fluorine interactions leading to spontaneous self-assembly into infinite columns with honeycomb-like lattices.

This article is part of the themed collection: 2023 Chemical Science Covers

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Article information

DOI: https://doi.org/10.1039/D2SC05348A
Article type: Edge Article
Submitted: 25 Sep 2022
Accepted: 13 Nov 2022
First published: 16 Nov 2022
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry

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Chem. Sci., 2023,14, 70-77

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Catalysis enabled synthesis, structures, and reactivities of fluorinated S₈-corona[n]arenes (n = 8–12)

Andrew. T. Turley, M. W. D. Hanson-Heine, Stephen. P. Argent, Y. Hu, Thomas. A. Jones, M. Fay and S. Woodward, Chem. Sci., 2023, 14, 70 DOI: 10.1039/D2SC05348A

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