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Requirements for Terpene Cyclizations inside the Supramolecular Resorcinarene Capsule: Bound Water and its Protonation Determine the Catalytic Activit

Merget, Severin and Catti, Lorenzo and Piccini, Giovanni-Maria and Tiefenbacher, Konrad. (2020) Requirements for Terpene Cyclizations inside the Supramolecular Resorcinarene Capsule: Bound Water and its Protonation Determine the Catalytic Activit. Journal of the American Chemical Society, 142 (9). pp. 4400-4410.

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Official URL: https://edoc.unibas.ch/81128/

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Abstract

he elucidation of the requirements for efficient catalysis within supramolecular host systems is an important prerequisite for developing novel supramolecular catalysts. The resorcinarene hexamer has recently been shown to be the first supramolecular catalyst to promote the tail-to-head terpene cyclization in a biomimetic fashion. We herein present the synthesis of a number of resorcinarene-based macrocycles composed of different ratios of resorcinol and pyrogallol units capable of self-assembly and compare the corresponding assemblies regarding their catalytic activity in the cyclization of monoterpenes. The assemblies were investigated in detail with respect to a number of properties including the encapsulation of substrate and ion pairs, the structural incorporation of water, and the response to externally added acid (HCl). The results obtained strongly indicate that water incorporated into the hydrogen-bond network of the self-assembled structure plays an integral role for catalysis, effectively acting as a proton shuttle to activate the encapsulated substrate. These findings are also supported by molecular dynamics simulations, providing further insight into the protonation pathway and the relative energies of the intermediates involved.
Faculties and Departments:05 Faculty of Science > Departement Chemie
05 Faculty of Science > Departement Chemie > Chemie > Synthesis of Functional Modules (Tiefenbacher)
UniBasel Contributors:Merget, Severin Florian and Piccini, GiovanniMaria and Tiefenbacher, Konrad
Item Type:Article, refereed
Article Subtype:Research Article
Publisher:American Chemical Society
ISSN:0002-7863
e-ISSN:1520-5126
Note:Publication type according to Uni Basel Research Database: Journal article
Language:English
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Last Modified:04 Mar 2021 02:30
Deposited On:16 Feb 2021 09:43

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