A combined experimental and theoretical study of the supramolecular self-assembly of the natural benzopyran 2,2-dimethyl-3-hydroxy-6-acetyl-chromane and its isomeric benzofuran 10,11-dihydro-10-hydroxytremetone

Epoxidation of 4HMBA, the main metabolite of the medicinal plant <i>Sencecionutans</i>, produces an unstable epoxide eventually giving rise to a mixture of four derivatives, three of them previously reported as natural products. The epoxide product easily undergoes an intra-molecular att...

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Autores: Gil, Diego M., Lizarraga, E., Echeverría, Gustavo Alberto, Piro, Oscar Enrique, Catalán, C. A. N., Ben Altabef, A.
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2017
País:Argentina
Institución:Universidad Nacional de La Plata
Repositorio:SEDICI (UNLP)
Idioma:inglés
OAI Identifier:oai:sedici.unlp.edu.ar:10915/103111
Acceso en línea:http://sedici.unlp.edu.ar/handle/10915/103111
Access Level:acceso abierto
Palabra clave:Física
Chromane derivative
Crystal structure
IR and Raman spectroscopy
Hydrogen bonds
Quantum chemical calculations
Benzofuran derivative
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spelling A combined experimental and theoretical study of the supramolecular self-assembly of the natural benzopyran 2,2-dimethyl-3-hydroxy-6-acetyl-chromane and its isomeric benzofuran 10,11-dihydro-10-hydroxytremetoneGil, Diego M.Lizarraga, E.Echeverría, Gustavo AlbertoPiro, Oscar EnriqueCatalán, C. A. N.Ben Altabef, A.FísicaChromane derivativeCrystal structureIR and Raman spectroscopyHydrogen bondsQuantum chemical calculationsBenzofuran derivativeEpoxidation of 4HMBA, the main metabolite of the medicinal plant <i>Sencecionutans</i>, produces an unstable epoxide eventually giving rise to a mixture of four derivatives, three of them previously reported as natural products. The epoxide product easily undergoes an intra-molecular attack of the phenolic hydroxyl against the epoxide group carbons to produce either a benzofuran or a chromane derivative. When dissolved in methanol-water mixture at room temperature the epoxide is completely solvolyzed to give the corresponding diol (hydrolysis) or vicinal hydroxyl-methoxy (methanolysis) derivative. All the compounds involved in the above reactions were characterized by IR, Raman, H NMR and UV–vis spectroscopies, and by mass spectrometry. Density functional theory (DFT) computations were used to optimize the structure conformations. The optimized structures were further subjected to a Natural Bond Orbital (NBO) and electrostatic potentials analysis. The crystal structures of the title compounds (for short, 3 and 4 respectively) were determined by X-ray diffraction methods. Compound 3 crystallizes in the triclinic P-1 space group with a = 6.4289 (6) Å, b = 8.7120 (6) Å, c = 10.952 (1) Å, α = 92.280 (7)°, β = 95.738 (7)°, γ = 103.973 (7)°, and Z = 2 molecules per unit cell and 4 in the monoclinic P21/c space group with a = 11.2891 (6) Å, b = 9.1902 (4) Å, c = 12.4272 (7) Å. Β = 113.689 (7)°, and Z = 4. In 3 neighboring molecules are linked to each other by OH⋯O (keto) bonds giving rise to a polymeric structure. In 4 the OH group is a bifurcate H-bond donor. It forms a weak intra-molecular OH⋯O (furan) bond and also a much stronger inter-molecular OH⋯O (keto) bond giving rise to a zig-zag polymeric structure. A detailed analysis of the solid state molecular interactions of compounds 3 and 4 has been performed using Hirshfeld surface analysis and their associated 2D fingerprint plots.Instituto de Física La Plata2017-06info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionArticulohttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdf164-178http://sedici.unlp.edu.ar/handle/10915/103111enginfo:eu-repo/semantics/altIdentifier/url/https://www.sciencedirect.com/science/article/abs/pii/S0022286017307573?via%3Dihubinfo:eu-repo/semantics/altIdentifier/issn/0022-2860info:eu-repo/semantics/altIdentifier/doi/10.1016/j.molstruc.2017.05.137info:eu-repo/semantics/openAccesshttp://creativecommons.org/licenses/by-nc-sa/4.0/Creative Commons Attribution-NonCommercial-ShareAlike 4.0 International (CC BY-NC-SA 4.0)reponame:SEDICI (UNLP)instname:Universidad Nacional de La Platainstacron:UNLP2024-05-08T13:00:14Zoai:sedici.unlp.edu.ar:10915/103111Institucionalhttp://sedici.unlp.edu.ar/Universidad públicaNo correspondehttp://sedici.unlp.edu.ar/oai/snrdalira@sedici.unlp.edu.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:13292024-05-08 13:00:14.852SEDICI (UNLP) - Universidad Nacional de La Platafalse
dc.title.none.fl_str_mv A combined experimental and theoretical study of the supramolecular self-assembly of the natural benzopyran 2,2-dimethyl-3-hydroxy-6-acetyl-chromane and its isomeric benzofuran 10,11-dihydro-10-hydroxytremetone
title A combined experimental and theoretical study of the supramolecular self-assembly of the natural benzopyran 2,2-dimethyl-3-hydroxy-6-acetyl-chromane and its isomeric benzofuran 10,11-dihydro-10-hydroxytremetone
spellingShingle A combined experimental and theoretical study of the supramolecular self-assembly of the natural benzopyran 2,2-dimethyl-3-hydroxy-6-acetyl-chromane and its isomeric benzofuran 10,11-dihydro-10-hydroxytremetone
Gil, Diego M.
Física
Chromane derivative
Crystal structure
IR and Raman spectroscopy
Hydrogen bonds
Quantum chemical calculations
Benzofuran derivative
title_short A combined experimental and theoretical study of the supramolecular self-assembly of the natural benzopyran 2,2-dimethyl-3-hydroxy-6-acetyl-chromane and its isomeric benzofuran 10,11-dihydro-10-hydroxytremetone
title_full A combined experimental and theoretical study of the supramolecular self-assembly of the natural benzopyran 2,2-dimethyl-3-hydroxy-6-acetyl-chromane and its isomeric benzofuran 10,11-dihydro-10-hydroxytremetone
title_fullStr A combined experimental and theoretical study of the supramolecular self-assembly of the natural benzopyran 2,2-dimethyl-3-hydroxy-6-acetyl-chromane and its isomeric benzofuran 10,11-dihydro-10-hydroxytremetone
title_full_unstemmed A combined experimental and theoretical study of the supramolecular self-assembly of the natural benzopyran 2,2-dimethyl-3-hydroxy-6-acetyl-chromane and its isomeric benzofuran 10,11-dihydro-10-hydroxytremetone
title_sort A combined experimental and theoretical study of the supramolecular self-assembly of the natural benzopyran 2,2-dimethyl-3-hydroxy-6-acetyl-chromane and its isomeric benzofuran 10,11-dihydro-10-hydroxytremetone
dc.creator.none.fl_str_mv Gil, Diego M.
Lizarraga, E.
Echeverría, Gustavo Alberto
Piro, Oscar Enrique
Catalán, C. A. N.
Ben Altabef, A.
author Gil, Diego M.
author_facet Gil, Diego M.
Lizarraga, E.
Echeverría, Gustavo Alberto
Piro, Oscar Enrique
Catalán, C. A. N.
Ben Altabef, A.
author_role author
author2 Lizarraga, E.
Echeverría, Gustavo Alberto
Piro, Oscar Enrique
Catalán, C. A. N.
Ben Altabef, A.
author2_role author
author
author
author
author
dc.subject.none.fl_str_mv Física
Chromane derivative
Crystal structure
IR and Raman spectroscopy
Hydrogen bonds
Quantum chemical calculations
Benzofuran derivative
topic Física
Chromane derivative
Crystal structure
IR and Raman spectroscopy
Hydrogen bonds
Quantum chemical calculations
Benzofuran derivative
description Epoxidation of 4HMBA, the main metabolite of the medicinal plant <i>Sencecionutans</i>, produces an unstable epoxide eventually giving rise to a mixture of four derivatives, three of them previously reported as natural products. The epoxide product easily undergoes an intra-molecular attack of the phenolic hydroxyl against the epoxide group carbons to produce either a benzofuran or a chromane derivative. When dissolved in methanol-water mixture at room temperature the epoxide is completely solvolyzed to give the corresponding diol (hydrolysis) or vicinal hydroxyl-methoxy (methanolysis) derivative. All the compounds involved in the above reactions were characterized by IR, Raman, H NMR and UV–vis spectroscopies, and by mass spectrometry. Density functional theory (DFT) computations were used to optimize the structure conformations. The optimized structures were further subjected to a Natural Bond Orbital (NBO) and electrostatic potentials analysis. The crystal structures of the title compounds (for short, 3 and 4 respectively) were determined by X-ray diffraction methods. Compound 3 crystallizes in the triclinic P-1 space group with a = 6.4289 (6) Å, b = 8.7120 (6) Å, c = 10.952 (1) Å, α = 92.280 (7)°, β = 95.738 (7)°, γ = 103.973 (7)°, and Z = 2 molecules per unit cell and 4 in the monoclinic P21/c space group with a = 11.2891 (6) Å, b = 9.1902 (4) Å, c = 12.4272 (7) Å. Β = 113.689 (7)°, and Z = 4. In 3 neighboring molecules are linked to each other by OH⋯O (keto) bonds giving rise to a polymeric structure. In 4 the OH group is a bifurcate H-bond donor. It forms a weak intra-molecular OH⋯O (furan) bond and also a much stronger inter-molecular OH⋯O (keto) bond giving rise to a zig-zag polymeric structure. A detailed analysis of the solid state molecular interactions of compounds 3 and 4 has been performed using Hirshfeld surface analysis and their associated 2D fingerprint plots.
publishDate 2017
dc.date.none.fl_str_mv 2017-06
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
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dc.identifier.none.fl_str_mv http://sedici.unlp.edu.ar/handle/10915/103111
url http://sedici.unlp.edu.ar/handle/10915/103111
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/https://www.sciencedirect.com/science/article/abs/pii/S0022286017307573?via%3Dihub
info:eu-repo/semantics/altIdentifier/issn/0022-2860
info:eu-repo/semantics/altIdentifier/doi/10.1016/j.molstruc.2017.05.137
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
http://creativecommons.org/licenses/by-nc-sa/4.0/
Creative Commons Attribution-NonCommercial-ShareAlike 4.0 International (CC BY-NC-SA 4.0)
eu_rights_str_mv openAccess
rights_invalid_str_mv http://creativecommons.org/licenses/by-nc-sa/4.0/
Creative Commons Attribution-NonCommercial-ShareAlike 4.0 International (CC BY-NC-SA 4.0)
dc.format.none.fl_str_mv application/pdf
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instname_str Universidad Nacional de La Plata
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repository.name.fl_str_mv SEDICI (UNLP) - Universidad Nacional de La Plata
repository.mail.fl_str_mv alira@sedici.unlp.edu.ar
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