Catalysis enabled synthesis, structures, and reactivities of fluorinated s8-corona[n]arenes (n = 8-12)

DOI: 10.1039/D2SC05348A

Authors: Simon Woodward (University of Nottingham) , Andrew Turley (University of Nottingham) , Magnus W. D. Hanson-Heine (University of Nottingham) , Stephen Argent (University of Nottingham) , Yaoyang Hu (University of Nottingham) , Thomas A. Jones (University of Nottingham) , Michael Fay (University of Nottingham)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Chemical Science

State: Published (Approved)
Published: November 2022
Diamond Proposal Number(s): 21755 , 28766

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 subsitution 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.

Subject Areas: Chemistry


Instruments: I19-Small Molecule Single Crystal Diffraction

Added On: 16/11/2022 16:27

Discipline Tags:

Physical Chemistry Catalysis Chemistry Organic Chemistry

Technical Tags:

Diffraction Single Crystal X-ray Diffraction (SXRD)