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A Concise Synthesis of a Methyl Ester 2-Resorcinarene: A Chair-Conformation Macrocycle

preprint
submitted on 20.03.2021, 13:25 and posted on 22.03.2021, 11:36 by Michael R. Reynolds, Fraser S. Pick, John Hayward, John F. Trant
Anions are important hydrogen bond acceptors in a range of biological, chemical, environmental and medical molecular recognition processes. These interactions have been exploited for the design and synthesis of ditopic resorcinarenes as the hydrogen bond strength can be tuned through the modification of the substituent at the 2-position. However, many potentially useful compounds, especially those incorporating electron-withdrawing functionalities, have not been prepared due to the challenge of their synthesis: their incorporation slows resorcinarene formation that is accessed by electrophic aromatic substitution. As part of our broader campaign to employ resorcinarenes as selective recognition elements, we need access to these specialized materials, and in this article we report a straightforward synthetic pathway for obtaining a 2-(carboxymethyl)-resorcinarene, and resorcinarene esters in general. We discuss the unusual conformation it adopts, and propose that this arises from the electron-withdrawing nature of the ester substituents that renders them better hydrogen bond acceptors than the phenols, ensuring that each of those acts as a donor only. DFT calculations show that this conformation arises as a consequence of the unusual configurational isomerism of this compound and interruption of the archetypal hydrogen bonding by the ester functionality.

Funding

Natural Sciences and Engineering Research Council of Canada 2018-06338

Canada Foundation for Innovation 37425

MITACS IT13760

History

Email Address of Submitting Author

j.trant@uwindsor.ca

Institution

University of Windsor

Country

Canada

ORCID For Submitting Author

0000-0002-4780-4968

Declaration of Conflict of Interest

The authors declare no conflicts of interest

Version Notes

Version 1.0

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