Just Add Water: Modulating the Structure-Derived Acidity of Catalytic Hexameric Resorcinarene Capsules

D.A. Poole, S. Mathew, J.N.H. Reek

Research output: Contribution to JournalArticleAcademicpeer-review

Abstract

© The hexameric undecyl-resorcin[4]arene capsule (C11R6) features eight discrete structural water molecules located at the vertices of its cubic suprastructure. Combining NMR spectroscopy with classical molecular dynamics (MD), we identified and characterized two distinct species of this capsule, C11R6-A and C11R6-B, respectively featuring 8 and 15 water molecules incorporated into their respective hydrogen-bonded networks. Furthermore, we found that the ratio of the C11R6-A and C11R6-B found in solution can be modulated by controlling the water content of the sample. The importance of this supramolecular modulation in C11R6 capsules is highlighted by its ability to perform acid-catalyzed transformations, which is an emergent property arising from the hydrogen bonding within the suprastructure. We show that the conversion of C11R6-A to C11R6-B enhances the catalytic rate of a model Diels-Alder cyclization by 10-fold, demonstrating the cofactor-derived control of a supramolecular catalytic process that emulates natural enzymatic systems.
Original languageEnglish
Pages (from-to)16419-16427
JournalJournal of the American Chemical Society
Volume143
Issue number40
DOIs
Publication statusPublished - 13 Oct 2021
Externally publishedYes

Funding

We thank our colleagues Dr. Anne Jans, Eline Meijer, and Dr. Andreas Ehlers for their assistance and advice for this study. We thank the European Research Council (ERC Adv. Grant 339786-5354 NAT_CAT) and the sustainable chemistry research program from the University of Amsterdam for financial support.

FundersFunder number
European Research Council339786-5354 NAT_CAT
Universiteit van Amsterdam

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