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

• Published in: Chemical science (Cambridge) 2022-12, Vol.14 (1), p.70-77
• Main Authors: Turley, Andrew T, Hanson-Heine, Magnus W D, Argent, Stephen P, Hu, Yaoyang, Jones, Thomas A, Fay, Michael, Woodward, Simon
• Format: Article
• Language: English
• ISSN: 2041-6520; 2041-6539
• DOI: 10.1039/d2sc05348a

Previously inaccessible large S -corona[ ]arene macrocycles ( = 8-12) with alternating aryl and 1,4-C F 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 Ar substitution protocols (catalytic NR F in pyridine, R = H, Me, Bu). Macrocycle size and functionality are tunable by precursor and catalyst selection. Equivalent simple NR F catalysis allows facile late-stage S Ar difunctionalisation of the ring C F 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 NR F 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.