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...
| Autores principales: | , , , , , |
|---|---|
| Formato: | Articulo |
| Lenguaje: | Inglés |
| Publicado: |
2017
|
| Materias: | |
| Acceso en línea: | http://sedici.unlp.edu.ar/handle/10915/103111 https://www.sciencedirect.com/science/article/abs/pii/S0022286017307573?via%3Dihub |
| Aporte de: |
| id |
I19-R120-10915-103111 |
|---|---|
| record_format |
dspace |
| institution |
Universidad Nacional de La Plata |
| institution_str |
I-19 |
| repository_str |
R-120 |
| collection |
SEDICI (UNLP) |
| language |
Inglés |
| topic |
Física Chromane derivative Crystal structure IR and Raman spectroscopy Hydrogen bonds Quantum chemical calculations Benzofuran derivative |
| spellingShingle |
Física Chromane derivative Crystal structure IR and Raman spectroscopy Hydrogen bonds Quantum chemical calculations Benzofuran derivative Gil, Diego M. Lizarraga, E. Echeverría, Gustavo Alberto Piro, Oscar Enrique Catalán, C. A. N. Ben Altabef, A. 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 |
| topic_facet |
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. |
| format |
Articulo Articulo |
| author |
Gil, Diego M. Lizarraga, E. Echeverría, Gustavo Alberto Piro, Oscar Enrique Catalán, C. A. N. Ben Altabef, A. |
| author_facet |
Gil, Diego M. Lizarraga, E. Echeverría, Gustavo Alberto Piro, Oscar Enrique Catalán, C. A. N. Ben Altabef, A. |
| author_sort |
Gil, Diego M. |
| 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 |
| 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 |
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 |
| publishDate |
2017 |
| url |
http://sedici.unlp.edu.ar/handle/10915/103111 https://www.sciencedirect.com/science/article/abs/pii/S0022286017307573?via%3Dihub |
| work_keys_str_mv |
AT gildiegom acombinedexperimentalandtheoreticalstudyofthesupramolecularselfassemblyofthenaturalbenzopyran22dimethyl3hydroxy6acetylchromaneanditsisomericbenzofuran1011dihydro10hydroxytremetone AT lizarragae acombinedexperimentalandtheoreticalstudyofthesupramolecularselfassemblyofthenaturalbenzopyran22dimethyl3hydroxy6acetylchromaneanditsisomericbenzofuran1011dihydro10hydroxytremetone AT echeverriagustavoalberto acombinedexperimentalandtheoreticalstudyofthesupramolecularselfassemblyofthenaturalbenzopyran22dimethyl3hydroxy6acetylchromaneanditsisomericbenzofuran1011dihydro10hydroxytremetone AT pirooscarenrique acombinedexperimentalandtheoreticalstudyofthesupramolecularselfassemblyofthenaturalbenzopyran22dimethyl3hydroxy6acetylchromaneanditsisomericbenzofuran1011dihydro10hydroxytremetone AT catalancan acombinedexperimentalandtheoreticalstudyofthesupramolecularselfassemblyofthenaturalbenzopyran22dimethyl3hydroxy6acetylchromaneanditsisomericbenzofuran1011dihydro10hydroxytremetone AT benaltabefa acombinedexperimentalandtheoreticalstudyofthesupramolecularselfassemblyofthenaturalbenzopyran22dimethyl3hydroxy6acetylchromaneanditsisomericbenzofuran1011dihydro10hydroxytremetone AT gildiegom combinedexperimentalandtheoreticalstudyofthesupramolecularselfassemblyofthenaturalbenzopyran22dimethyl3hydroxy6acetylchromaneanditsisomericbenzofuran1011dihydro10hydroxytremetone AT lizarragae combinedexperimentalandtheoreticalstudyofthesupramolecularselfassemblyofthenaturalbenzopyran22dimethyl3hydroxy6acetylchromaneanditsisomericbenzofuran1011dihydro10hydroxytremetone AT echeverriagustavoalberto combinedexperimentalandtheoreticalstudyofthesupramolecularselfassemblyofthenaturalbenzopyran22dimethyl3hydroxy6acetylchromaneanditsisomericbenzofuran1011dihydro10hydroxytremetone AT pirooscarenrique combinedexperimentalandtheoreticalstudyofthesupramolecularselfassemblyofthenaturalbenzopyran22dimethyl3hydroxy6acetylchromaneanditsisomericbenzofuran1011dihydro10hydroxytremetone AT catalancan combinedexperimentalandtheoreticalstudyofthesupramolecularselfassemblyofthenaturalbenzopyran22dimethyl3hydroxy6acetylchromaneanditsisomericbenzofuran1011dihydro10hydroxytremetone AT benaltabefa combinedexperimentalandtheoreticalstudyofthesupramolecularselfassemblyofthenaturalbenzopyran22dimethyl3hydroxy6acetylchromaneanditsisomericbenzofuran1011dihydro10hydroxytremetone |
| bdutipo_str |
Repositorios |
| _version_ |
1764820441518571522 |