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Enaminone Substituted Resorcin[4]arene-Sealing of an Upper-Rim with a Directional System of Hydrogen-Bonds.

ABSTRACT: The paper presents the synthesis of an enaminone resorcin[4]arene via a thermally activated o-quinomethide. The crystal structure indicates that in the solid state all enaminone units participate in a unidirectional seam of 12 intramolecular hydrogen bonds that are formed around the cavity. The molecule exhibits C2 symmetry, with two opposite-laying enaminone units directed inside the cavity ("in"), and the other two units outside the cavity ("out"). In the solution the enaminone resorcin[4]arene exists as a mixture of conformers with distribution controlled by temperature and solvent. The experimental data are compared with the results of theoretical calculations using DFT B3LYP/6-31G(d,p) and fast semi-empirical DFTB/GFN2-xTB method in various solvents.

SUBMITTER: Szafraniec A

PROVIDER: S-EPMC7589316 | biostudies-literature | 2020 Oct

REPOSITORIES: biostudies-literature

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Enaminone Substituted Resorcin[4]arene-Sealing of an Upper-Rim with a Directional System of Hydrogen-Bonds.

Szafraniec Anna A Grajda Marcin M Jędrzejewska Hanna H Szumna Agnieszka A Iwanek Waldemar W

International journal of molecular sciences 20201011 20

The paper presents the synthesis of an enaminone resorcin[4]arene via a thermally activated o-quinomethide. The crystal structure indicates that in the solid state all enaminone units participate in a unidirectional seam of 12 intramolecular hydrogen bonds that are formed around the cavity. The molecule exhibits C2 symmetry, with two opposite-laying enaminone units directed inside the cavity ("in"), and the other two units outside the cavity ("out</i ...[more]

PMID: 33050670

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Intramolecular Hydrogen Bond Driven Conformational Selectivity of Coumarin Derivatives of Resorcin[4]arene.

Project description:In this study, the synthesis and structure of 4-aminocoumarin derivatives of resorcin[4]arene were investigated. Spectroscopic analysis and quantum mechanical calculations showed that this molecule undertakes a crown-in conformation in chloroform. The conformations of the aminocoumarin derivative of resorcin[4]arene were compared with a hydroxycoumarin derivative of resorcin[4]arene, and the effect of the substituent on the conformational selectivity of the coumarin derivatives of resorcin[4]arene was demonstrated. Both UV-VIS and fluorescence spectroscopy for the coumarin derivative of resorcin[4]arene (3) were performed, and a strong fluorescence quenching of derivative 3 compared to 4-aminocoumarin was observed.

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Binding Properties and Supramolecular Polymerization of a Water-Soluble Resorcin[4]arene.

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Resorcin[4]arene-based multidentate phosphate ligands with superior binding affinity for nanocrystal surfaces.

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Enantioselective Tail-to-Head Terpene Cyclizations by Optically Active Hexameric Resorcin[4]arene Capsule Derivatives.

Project description:Molecular capsules enable the conversion of substrates inside a closed cavity, mimicking to some extent enzymatic catalysis. Chirality transfer from the molecular capsule onto the encapsulated substrate has been only studied in a few cases. Here we demonstrate that chirality transfer is possible inside a rather large molecular container of approximately 1400 Å3 . Specifically, we present 1) the first examples of optically active hexameric resorcin[4]arene capsules, 2) their ability to enantioselectively catalyze tail-to-head terpene cyclizations, and 3) the surprisingly high sensitivity of enantioselectivity on the structural modifications.

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A resorcin[4]arene hexameric capsule as a supramolecular catalyst in elimination and isomerization reactions.

Project description:The hexameric resorcin[4]arene capsule as a self-assembled organocatalyst promotes a series of reactions like the carbonyl-ene cyclization of (S)-citronellal preferentially to isopulegol, the water elimination from 1,1-diphenylethanol, the isomerization of α-pinene and β-pinene preferentially to limonene and minor amounts of camphene. The role of the supramolecular catalyst consists in promoting the protonation of the substrates leading to the formation of cationic intermediates that are stabilized within the cavity with consequent peculiar features in terms of acceleration and product selectivity. In all cases the catalytic activity displayed by the hexameric capsule is remarkable if compared to many other strong Brønsted or Lewis acids.

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