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A Study about Regioisomeric Hydroquinones with Multiple Intramolecular Hydrogen Bonding

A theoretical exploration about hydrogen bonding in a series of synthetic regioisomeric antitumor tricyclic hydroquinones is presented. The stabilization energy for the intramolecular hydrogen bond (IHB) formation in four structurally different situations were evaluated: (a) IHB between the proton o...

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Autores principales: Martínez-Cifuentes, Maximiliano, Cardona, Wilson, Saitz, Claudio, Weiss-López, Boris, Araya-Maturana, Ramiro
Formato: Online Artículo Texto
Lenguaje:English
Publicado: MDPI 2017
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6153943/
https://www.ncbi.nlm.nih.gov/pubmed/28387716
http://dx.doi.org/10.3390/molecules22040593
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author Martínez-Cifuentes, Maximiliano
Cardona, Wilson
Saitz, Claudio
Weiss-López, Boris
Araya-Maturana, Ramiro
author_facet Martínez-Cifuentes, Maximiliano
Cardona, Wilson
Saitz, Claudio
Weiss-López, Boris
Araya-Maturana, Ramiro
author_sort Martínez-Cifuentes, Maximiliano
collection PubMed
description A theoretical exploration about hydrogen bonding in a series of synthetic regioisomeric antitumor tricyclic hydroquinones is presented. The stabilization energy for the intramolecular hydrogen bond (IHB) formation in four structurally different situations were evaluated: (a) IHB between the proton of a phenolic hydroxyl group and an ortho-carbonyl group (forming a six-membered ring); (b) between the oxygen atom of a phenolic hydroxyl group and the proton of an hydroxyalkyl group (seven membered ring); (c) between the proton of a phenolic hydroxyl group with the oxygen atom of the hydroxyl group of a hydroxyalkyl moiety (seven-membered ring); and (d) between the proton of a phenolic hydroxyl group and an oxygen atom directly bonded to the aromatic ring in ortho position (five-membered ring). A conformational analysis for the rotation around the hydroxyalkyl substituent is also performed. It is observed that there is a correspondence between the conformational energies and the IHB. The strongest intramolecular hydrogen bonds are those involving a phenolic proton and a carbonyl oxygen atom, forming a six-membered ring, and the weakest are those involving a phenolic proton with the oxygen atom of the chromenone, forming five-membered rings. Additionally, the synthesis and structural assignment of two pairs of regioisomeric hydroquinones, by 2D-NMR experiments, are reported. These results can be useful in the design of biologically-active molecules.
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spelling pubmed-61539432018-11-13 A Study about Regioisomeric Hydroquinones with Multiple Intramolecular Hydrogen Bonding Martínez-Cifuentes, Maximiliano Cardona, Wilson Saitz, Claudio Weiss-López, Boris Araya-Maturana, Ramiro Molecules Article A theoretical exploration about hydrogen bonding in a series of synthetic regioisomeric antitumor tricyclic hydroquinones is presented. The stabilization energy for the intramolecular hydrogen bond (IHB) formation in four structurally different situations were evaluated: (a) IHB between the proton of a phenolic hydroxyl group and an ortho-carbonyl group (forming a six-membered ring); (b) between the oxygen atom of a phenolic hydroxyl group and the proton of an hydroxyalkyl group (seven membered ring); (c) between the proton of a phenolic hydroxyl group with the oxygen atom of the hydroxyl group of a hydroxyalkyl moiety (seven-membered ring); and (d) between the proton of a phenolic hydroxyl group and an oxygen atom directly bonded to the aromatic ring in ortho position (five-membered ring). A conformational analysis for the rotation around the hydroxyalkyl substituent is also performed. It is observed that there is a correspondence between the conformational energies and the IHB. The strongest intramolecular hydrogen bonds are those involving a phenolic proton and a carbonyl oxygen atom, forming a six-membered ring, and the weakest are those involving a phenolic proton with the oxygen atom of the chromenone, forming five-membered rings. Additionally, the synthesis and structural assignment of two pairs of regioisomeric hydroquinones, by 2D-NMR experiments, are reported. These results can be useful in the design of biologically-active molecules. MDPI 2017-04-07 /pmc/articles/PMC6153943/ /pubmed/28387716 http://dx.doi.org/10.3390/molecules22040593 Text en © 2017 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (http://creativecommons.org/licenses/by/4.0/).
spellingShingle Article
Martínez-Cifuentes, Maximiliano
Cardona, Wilson
Saitz, Claudio
Weiss-López, Boris
Araya-Maturana, Ramiro
A Study about Regioisomeric Hydroquinones with Multiple Intramolecular Hydrogen Bonding
title A Study about Regioisomeric Hydroquinones with Multiple Intramolecular Hydrogen Bonding
title_full A Study about Regioisomeric Hydroquinones with Multiple Intramolecular Hydrogen Bonding
title_fullStr A Study about Regioisomeric Hydroquinones with Multiple Intramolecular Hydrogen Bonding
title_full_unstemmed A Study about Regioisomeric Hydroquinones with Multiple Intramolecular Hydrogen Bonding
title_short A Study about Regioisomeric Hydroquinones with Multiple Intramolecular Hydrogen Bonding
title_sort study about regioisomeric hydroquinones with multiple intramolecular hydrogen bonding
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6153943/
https://www.ncbi.nlm.nih.gov/pubmed/28387716
http://dx.doi.org/10.3390/molecules22040593
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