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

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

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 SNAr 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 SNAr 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.

Citation

Turley, A. T., Hanson-Heine, M. W. D., Argent, S. P., Hu, Y., Jones, T. A., Fay, M., & Woodward, S. (2023). Catalysis enabled synthesis, structures, and reactivities of fluorinated S8-corona[n]arenes (n = 8–12). Chemical Science, 14(1), 70-77. https://doi.org/10.1039/d2sc05348a

• Journal Article Type: Article
• Acceptance Date: Nov 13, 2022
• Online Publication Date: Nov 16, 2022
• Publication Date: Jan 7, 2023
• Deposit Date: Dec 20, 2022
• Publicly Available Date: Dec 20, 2022
• Journal: Chemical Science
• Print ISSN: 2041-6520
• Electronic ISSN: 2041-6539
• Publisher: Royal Society of Chemistry
• Peer Reviewed: Peer Reviewed
• Volume: 14
• Issue: 1
• Pages: 70-77
• DOI: https://doi.org/10.1039/d2sc05348a
• Public URL: https://nottingham-repository.worktribe.com/output/14602518
• Publisher URL: https://pubs.rsc.org/en/content/articlelanding/2023/SC/D2SC05348A