Fixing the conformation of calix[4]arenes: When are three carbons not enough?

Matthews, Susan ORCID: https://orcid.org/0000-0001-8821-0851, Cecioni, Samy, O'Brien, John, MacDonald, Colin, Hughes, David, Jones, Garth, Ashworth, Stephen ORCID: https://orcid.org/0000-0003-4213-3541 and Vidal, Sebastien (2018) Fixing the conformation of calix[4]arenes: When are three carbons not enough? Chemistry - A European Journal, 24 (17). pp. 4436-4444. ISSN 0947-6539

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Abstract

Calix[4]arenes are unique macrocycles that through judicious functionalisation at the lower-rim can be either fixed in one of four conformations or remain conformationally flexible. Introduction of propynyl or propenyl groups unexpectedly provides a new possibility; a unidirectional conformational switch, with the 1,3-alternate and 1,2-alternate conformers switching to the partial cone conformation, whilst the cone conformation is unchanged, under standard experimental conditions. Using 1H NMR kinetic studies, rates of switching have been shown to be dependent on the starting conformation, upper-rim substituent, where reduction in bulk enables faster switching, solvent and temperature with 1,2-alternate conformations switching fastest. Ab initio calculations (DFT) confirmed the relative stabilities of the conformations and point towards the partial cone conformer being the most stable of the four. The potential impact on synthesis through the ‘click’ reaction has been investigated and found not to be significant.

Item Type:	Article
Uncontrolled Keywords:	nmr spectroscopy,calixarenes,macrocycles,kinetics,conformational analysis
Faculty \ School:	Faculty of Science > School of Pharmacy (former - to 2024) Faculty of Science Faculty of Science > School of Chemistry (former - to 2024) Faculty of Science > School of Natural Sciences (former - to 2024)
UEA Research Groups:	Faculty of Science > Research Groups > Centre for Ocean and Atmospheric Sciences Faculty of Science > Research Groups > Chemical Biology and Medicinal Chemistry (former - to 2021) Faculty of Science > Research Groups > Chemistry of Light and Energy Faculty of Science > Research Groups > Centre for Photonics and Quantum Science
Depositing User:	Pure Connector
Date Deposited:	17 Jan 2018 17:30
Last Modified:	25 Sep 2024 13:13
URI:	https://ueaeprints.uea.ac.uk/id/eprint/65982
DOI:	10.1002/chem.201705955

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