Estudio computacional del rearreglo sigmatrópico [1,3] de la (Z)-3-(4-(dimetilamino)bencilidén)tiocroman-4-ona

En el presente trabajo se realizó un estudio computacional de un rearreglo sigmatrópico [1,3] de hidrógeno intramolecular para la (Z)-3-(4-(dimetilamino)-bencilidén)tiocroman-4-ona, aplicando la Teoría del Funcional de la Densidad con el funcional de intercambio-correlación B3LYP y el conjunto de fu...

Full description

Autores:
Núñez, Jesús
Márquez, Edgar
Rivas, Carlos
Urdaneta, Neudo
Tipo de recurso:
Article of investigation
Fecha de publicación:
2017
Institución:
Corporación Universidad de la Costa
Repositorio:
REDICUC - Repositorio CUC
Idioma:
spa
OAI Identifier:
oai:repositorio.cuc.edu.co:11323/10741
Acceso en línea:
https://hdl.handle.net/11323/10741
https://repositorio.cuc.edu.co/
Palabra clave:
3-bencilidéntiocroman-4-ona
Rearreglo sigmatrópico
TFD
Estado de transición
3-Benzylidenethiochroman-4-one
Sigmatropic rearrangement
DFT
Transition state
Rights
openAccess
License
Atribución-NoComercial-CompartirIgual 4.0 Internacional (CC BY-NC-SA 4.0)
id RCUC2_535c1d772ccad32386c08d797e2c99d3
oai_identifier_str oai:repositorio.cuc.edu.co:11323/10741
network_acronym_str RCUC2
network_name_str REDICUC - Repositorio CUC
repository_id_str
dc.title.spa.fl_str_mv Estudio computacional del rearreglo sigmatrópico [1,3] de la (Z)-3-(4-(dimetilamino)bencilidén)tiocroman-4-ona
dc.title.translated.none.fl_str_mv Computational study of [1,3] sigmatropic rearrangement of the (Z)-3-(4-(dimethylamino)benzyliden)thiocroman-4- one
title Estudio computacional del rearreglo sigmatrópico [1,3] de la (Z)-3-(4-(dimetilamino)bencilidén)tiocroman-4-ona
spellingShingle Estudio computacional del rearreglo sigmatrópico [1,3] de la (Z)-3-(4-(dimetilamino)bencilidén)tiocroman-4-ona
3-bencilidéntiocroman-4-ona
Rearreglo sigmatrópico
TFD
Estado de transición
3-Benzylidenethiochroman-4-one
Sigmatropic rearrangement
DFT
Transition state
title_short Estudio computacional del rearreglo sigmatrópico [1,3] de la (Z)-3-(4-(dimetilamino)bencilidén)tiocroman-4-ona
title_full Estudio computacional del rearreglo sigmatrópico [1,3] de la (Z)-3-(4-(dimetilamino)bencilidén)tiocroman-4-ona
title_fullStr Estudio computacional del rearreglo sigmatrópico [1,3] de la (Z)-3-(4-(dimetilamino)bencilidén)tiocroman-4-ona
title_full_unstemmed Estudio computacional del rearreglo sigmatrópico [1,3] de la (Z)-3-(4-(dimetilamino)bencilidén)tiocroman-4-ona
title_sort Estudio computacional del rearreglo sigmatrópico [1,3] de la (Z)-3-(4-(dimetilamino)bencilidén)tiocroman-4-ona
dc.creator.fl_str_mv Núñez, Jesús
Márquez, Edgar
Rivas, Carlos
Urdaneta, Neudo
dc.contributor.author.none.fl_str_mv Núñez, Jesús
Márquez, Edgar
Rivas, Carlos
Urdaneta, Neudo
dc.subject.proposal.spa.fl_str_mv 3-bencilidéntiocroman-4-ona
Rearreglo sigmatrópico
TFD
Estado de transición
topic 3-bencilidéntiocroman-4-ona
Rearreglo sigmatrópico
TFD
Estado de transición
3-Benzylidenethiochroman-4-one
Sigmatropic rearrangement
DFT
Transition state
dc.subject.proposal.eng.fl_str_mv 3-Benzylidenethiochroman-4-one
Sigmatropic rearrangement
DFT
Transition state
description En el presente trabajo se realizó un estudio computacional de un rearreglo sigmatrópico [1,3] de hidrógeno intramolecular para la (Z)-3-(4-(dimetilamino)-bencilidén)tiocroman-4-ona, aplicando la Teoría del Funcional de la Densidad con el funcional de intercambio-correlación B3LYP y el conjunto de funciones base 6-31G(d,p), a través del paquete computacional Gaussian 09W. Se evaluaron dos posibles migraciones suprafaciales y antarafaciales del átomo de hidrógeno unido al anillo tiopiran-4-ona de la (Z)-3-(4-(dimetilamino)-bencilidén)tiocroman-4-ona, encontrando una energía de activación 4 Kcal/mol más favorable para un estado de transición con características de un desplazamiento suprafacial [1,2], en comparación con la energía de activación de un estado de transición de un desplazamiento antarafacial [1,3].
publishDate 2017
dc.date.issued.none.fl_str_mv 2017-06-02
dc.date.accessioned.none.fl_str_mv 2024-02-20T14:04:42Z
dc.date.available.none.fl_str_mv 2024-02-20T14:04:42Z
dc.type.spa.fl_str_mv Artículo de revista
dc.type.coar.spa.fl_str_mv http://purl.org/coar/resource_type/c_2df8fbb1
dc.type.content.spa.fl_str_mv Text
dc.type.driver.spa.fl_str_mv info:eu-repo/semantics/article
dc.type.redcol.spa.fl_str_mv http://purl.org/redcol/resource_type/ART
dc.type.version.spa.fl_str_mv info:eu-repo/semantics/publishedVersion
dc.type.coarversion.spa.fl_str_mv http://purl.org/coar/version/c_970fb48d4fbd8a85
format http://purl.org/coar/resource_type/c_2df8fbb1
status_str publishedVersion
dc.identifier.citation.spa.fl_str_mv Núñez, J., Márquez, E., Rivas, C., & Urdaneta, N. (2018). Estudio computacional del rearreglo sigmatrópico [1,3] de la (Z)-3-(4-(dimetilamino) benciliden)tiocroman-4-ona. Avances en Química, 12(2 - 3), 23-30. Recuperado de http://erevistas.saber.ula.ve/index.php/avancesenquimica/article/view/10116
dc.identifier.issn.spa.fl_str_mv 0041994X
dc.identifier.uri.none.fl_str_mv https://hdl.handle.net/11323/10741
dc.identifier.instname.spa.fl_str_mv Corporación Universidad de la Costa
dc.identifier.reponame.spa.fl_str_mv REDICUC - Repositorio CUC
dc.identifier.repourl.spa.fl_str_mv https://repositorio.cuc.edu.co/
identifier_str_mv Núñez, J., Márquez, E., Rivas, C., & Urdaneta, N. (2018). Estudio computacional del rearreglo sigmatrópico [1,3] de la (Z)-3-(4-(dimetilamino) benciliden)tiocroman-4-ona. Avances en Química, 12(2 - 3), 23-30. Recuperado de http://erevistas.saber.ula.ve/index.php/avancesenquimica/article/view/10116
0041994X
Corporación Universidad de la Costa
REDICUC - Repositorio CUC
url https://hdl.handle.net/11323/10741
https://repositorio.cuc.edu.co/
dc.language.iso.spa.fl_str_mv spa
language spa
dc.relation.ispartofjournal.spa.fl_str_mv Avances en Quimica
dc.relation.references.spa.fl_str_mv 1. P Böhler, Ch Tamm. The homo-isoflavones, a new class of natural product. Isolation and structure of eucomin and eucomol. Tetrahedron Letters, 8, 3479-3483 (1967).
2. RE Finckh, Ch Tamm. The homo-isoflavones III. Isolation and structure of punctatin, 3,9-Dihydro-Punctatin, 4’-O-Methyl-3,9- dihydro-punctatin, 4’-Demethyl-eucomin and 4’-Demethyl-5-Omethyl-3,9-dihydro-eucomin. Experientia, 26, 472-473 (1970).
3. TM Hung, CV Thu, NT Dat, SW Ryoo, JH Lee, JC Kim, M Na, HJ Jung, K Bae, BS Min. Homoisoflavonoid derivatives from the roots of Ophiopogon japonicus and their in vitro antiinflammation activity. Bioorganic & Medicinal Chemistry Letters, 20, 2412-2416 (2010).
4. P Perjési, U Das, ED Clercq, J Balzarini, M Kawase, H Sakagami, JP Stables, T Lorand, Z Rozmer, JR Dimmock. Design, synthesis and antiproliferative activity of some 3- benzylidene-2,3-dihydro-1-benzopyran-4-ones which display selective toxicity for malignant cells. Eur. J. Medicinal Chemistry, 43, 839-845 (2008).
5. T Al Nakib, V Bezjak, MJ Meegan, R Chandy. Synthesis and antifungal activity of some 3-benzylidenechroman-4-ones, 3- benzylidenethiochroman-4-ones and 2-benzylidene-1-tetralones. Eur. J. Medicinal Chemistry, 25, 455-462 (1990).
6. YF Li, ZQ Liu, XY Luo. Properties of synthetic homoisoflavonoids to reduce oxidants and to protect linoleic acid and DNA against oxidation. Journal of Agricultural and Food Chemistry, 58, 4126-4131 (2010).
7. S Tait, AL Salvati, N Desideri, L Fiore. Antiviral activity of substituted homoisoflavonoids on enteroviruses. Antiviral Research, 72, 252-255 (2006).
8. AT Nguyen, J Fontaine, H Malonne, P Duez. Homoisoflavanones from Disporopsis aspera. Phytochemistry, 67, 2159-2163 (2006).
9. T Ishikawa, Y Oku, T Tanaka, T Kumamoto. An approach to Anti-HIV-1 active Calophyllum Coumarin synthesis: An enantioselective construction of 2,3-Dimethyl-4-chromanone ring by Quinine-assisted intramolecular Michael-type addition. Tetrahedron Letters, 40, 3777-3780 (1999).
10. A Lévai, Z Dinya, JB Schág, G Tóth, Á Szöllösy. Synthesis of 3-Benzyl-4-chromones and 3-Benzyl-1-thio-4-chromones. Pharmazie, 36, 465-466 (1981).
11. J Andrieux, DRH Barton, H Patin. Rhodium-catalysed isomerisation of some unsaturated organic substrates. J. Chem. Soc., Perkin Transactions 1, 4, 359-363 (1977).
12. J McMurry. Química Orgánica. Sexta Edición. Thomson (2004).
13. RB Woodward, R Hoffmann. Selection rules for sigmatro picreactions. J. Amer. Chem. Soc., 87, 2511-2513 (1965).
14. GB Gill. The application of the Woodward-Hoffman Orbital symmetry rules to concerted organic reactions. Quarterly Reviews Chemical Society, 22, 338-389 (1968).
15. WR Rodwell, WJ Bouma, L Radom. Ab inition studies of 1,3- sigmatropic rearrangements: Effect of basis set and electron correlation. Int. J. Quantum Chemistry, 18, 107-116 (1980).
16. Jr B A Hess, LJ Schaad, J Pancir. Theoretical Studies of [1,n]- sigmatropic rearrangements involving hydrogen transfer in simple methyl-substituted conjugated polyenes. J. Amer. Chem. Soc., 107, 149-154 (1985).
17. LR Domingo, M.J. Aurell, P. Pérez. Understanding the Polar Mechanism of the Ene Reaction. A DFT Study. Org. Biomol. Chem., 12, 7581-7590 (2014)
18. LR Domingo. Why Diels-Alder reactions are non-concerted processes. J. Chil. Chem. Soc., 59, 2615-2518 (2014)
19. LR Domingo, MJ Aurell, P Pérez. The mechanism of ionic Diels-Alder reactions. A DFT study of the oxa-Povarov reaction. RSC Adv., 4, 16567-16577 (2014).
20. D Yepes, JS Murray, P Pérez, LR Domingo, P Politzer, P Jaque. Complementarity of reaction force and electron localization function analyses of asynchronicity in bond formation in DielsAlder reactions. Phys. Chem. Chem. Phys., 16, 6726-6734 (2014).
21. LR Domingo. State of the Art of the Bonding Changes along the Diels-Alder Reaction between Butadiene and Ethylene. Refuting the Pericyclic Mechanism. Organic Chemistry: Current Research, 2, 120 (2013).
22. A Valkonen, K Laihia, E Kolehmainen, R Kauppinen, P Perjési. Structural studies of seven homoisoflavonoids, six thiohomoisoflavonoids, and four structurally related compounds. Structural Chemistry, 23, 209-217 (2012).
23. Gaussian 09W, Revision A.02, Gaussian, Inc., Pittsburgh PA, (2009).
24. E Márquez, J Mora, T Cordoba, G Chuchani. Theoretical Study of the Mechanism for the Gas-Phase Pyrolysis Kinetics of 2- Methylbenzyl Chloride. Int. J. Chemical Kinetics, 3, 537-546 (2011).
25. E Marquez, T Cordova, G Chuchani. DFT Study of the GasPhase Thermal Decomposition Kinetics of 2-Ethoxypyridine into 2-Pyridone. Int. J. Quantum Chemistry, 112, 724–730 (2012)
26. K Fukui. Formulation of the reaction coordinate. J. Physical Chemistry, 74, 4161-4163 (1970).
27. JP Foster, F Weinhold. Natural hybrid orbitals. J. Amer. Chem. Soc., 102, 7211-7218 (1980).
28. KB Wiberg. Application of the pople-santry-segal CNDO method to the cyclopropylcarbinyl and cyclobutyl cation and to bicyclobutane. Tetrahedron, 24, 1083-1096 (1968).
29. A Moyano, MA Pericas, E Valenti. A theoretical study on the mechanism of the thermal and the acid-catalyzed descarboxylation of 2-Oxetanones (-Lactones). J. Org. Chem., 54, 573-582 (1989).
30. O Francia. Síntesis y fotoquímica de tiocromonas para su posible uso en terapia fotodinámica antimicrobiana. Tesis de Licenciatura, Universidad Simón Bolívar, Sartenejas, Venezuela(2011).
31. CE Hudson, D J McAdoo. An ab initio study of substituent effects in [1,3]-hydrogen shifts. J. Org. Chem., 68, 2735-2740 (2003).
32. G Tóth, Å Szöllosy, A Lévai, G Oszbach, W Dietrich, H Kühne. Stereochemistry of 3-Arylideneflavanones and their thio analogues by the use of 3 J(CH) Couplings. Magnetic Resonance in Chemistry, 29, 801-804 (1991).
33. F Bernardi, MA Robb, HB Schlegel, G Tonachini. An MC-SCF study of [1,3] and [1,2] sigmatropic shifts in propene. J. Amer. Chem. Soc., 106, 1198-1202 (1984)
dc.relation.citationendpage.spa.fl_str_mv 30
dc.relation.citationstartpage.spa.fl_str_mv 23
dc.relation.citationissue.spa.fl_str_mv 2-3
dc.relation.citationvolume.spa.fl_str_mv 12
dc.rights.none.fl_str_mv © Copyright 2018 Elsevier B.V., All rights reserved.
dc.rights.license.spa.fl_str_mv Atribución-NoComercial-CompartirIgual 4.0 Internacional (CC BY-NC-SA 4.0)
dc.rights.uri.spa.fl_str_mv https://creativecommons.org/licenses/by-nc-sa/4.0/
dc.rights.accessrights.spa.fl_str_mv info:eu-repo/semantics/openAccess
dc.rights.coar.spa.fl_str_mv http://purl.org/coar/access_right/c_abf2
rights_invalid_str_mv Atribución-NoComercial-CompartirIgual 4.0 Internacional (CC BY-NC-SA 4.0)
© Copyright 2018 Elsevier B.V., All rights reserved.
https://creativecommons.org/licenses/by-nc-sa/4.0/
http://purl.org/coar/access_right/c_abf2
eu_rights_str_mv openAccess
dc.format.extent.spa.fl_str_mv 8 páginas
dc.format.mimetype.spa.fl_str_mv application/pdf
dc.publisher.spa.fl_str_mv Univerisdad de Los Andes
dc.publisher.place.spa.fl_str_mv Venezuela
dc.source.spa.fl_str_mv https://www.scopus.com/record/display.uri?eid=2-s2.0-85050232002&origin=inward&txGid=13e22fa7ea6a7cb64090d68001afaa07
institution Corporación Universidad de la Costa
bitstream.url.fl_str_mv https://repositorio.cuc.edu.co/bitstreams/fe27e347-042a-4956-b766-727559cbd639/download
https://repositorio.cuc.edu.co/bitstreams/2d36f633-3049-4029-a498-e2332eabb5f4/download
https://repositorio.cuc.edu.co/bitstreams/4ba50ebc-ee55-44f5-bec8-716e3234d636/download
https://repositorio.cuc.edu.co/bitstreams/6baeff36-6efb-4595-9b53-830e89cae4de/download
bitstream.checksum.fl_str_mv ab157ffd8cda1adeeafb8064d7913479
2f9959eaf5b71fae44bbf9ec84150c7a
99489f2f50cd3612c7478c97e50fcd67
d70512192c504b16858fac0034a030b0
bitstream.checksumAlgorithm.fl_str_mv MD5
MD5
MD5
MD5
repository.name.fl_str_mv Repositorio de la Universidad de la Costa CUC
repository.mail.fl_str_mv repdigital@cuc.edu.co
_version_ 1811760805729796096
spelling Atribución-NoComercial-CompartirIgual 4.0 Internacional (CC BY-NC-SA 4.0)© Copyright 2018 Elsevier B.V., All rights reserved.https://creativecommons.org/licenses/by-nc-sa/4.0/info:eu-repo/semantics/openAccesshttp://purl.org/coar/access_right/c_abf2Núñez, JesúsMárquez, EdgarRivas, CarlosUrdaneta, Neudo2024-02-20T14:04:42Z2024-02-20T14:04:42Z2017-06-02Núñez, J., Márquez, E., Rivas, C., & Urdaneta, N. (2018). Estudio computacional del rearreglo sigmatrópico [1,3] de la (Z)-3-(4-(dimetilamino) benciliden)tiocroman-4-ona. Avances en Química, 12(2 - 3), 23-30. Recuperado de http://erevistas.saber.ula.ve/index.php/avancesenquimica/article/view/101160041994Xhttps://hdl.handle.net/11323/10741Corporación Universidad de la CostaREDICUC - Repositorio CUChttps://repositorio.cuc.edu.co/En el presente trabajo se realizó un estudio computacional de un rearreglo sigmatrópico [1,3] de hidrógeno intramolecular para la (Z)-3-(4-(dimetilamino)-bencilidén)tiocroman-4-ona, aplicando la Teoría del Funcional de la Densidad con el funcional de intercambio-correlación B3LYP y el conjunto de funciones base 6-31G(d,p), a través del paquete computacional Gaussian 09W. Se evaluaron dos posibles migraciones suprafaciales y antarafaciales del átomo de hidrógeno unido al anillo tiopiran-4-ona de la (Z)-3-(4-(dimetilamino)-bencilidén)tiocroman-4-ona, encontrando una energía de activación 4 Kcal/mol más favorable para un estado de transición con características de un desplazamiento suprafacial [1,2], en comparación con la energía de activación de un estado de transición de un desplazamiento antarafacial [1,3].This research is based on a computational study of a [1,3] sigmatropic intramolecular hydrogen rearrangement for (Z)-3-(4-(dimethylamino)benzylidene)thiochroman-4-one, applying the Density Functional Theory with the exchangecorrelation functional B3LYP and 6-31G(d,p) set basis using software package Gaussian 09W. Two possible suprafacials and anatarafacials migrations of the hydrogen atom bonded to ring thiopyran-4-one of the (Z)-3-(4-(Dimethylamino)- benzylidene)thiochroman-4-one were evaluated, results show an activation energy of 4 Kcal/mol which is more favorable for a transition state featuring characteristics related to a [1,2] suprafacial shift, in comparison with the amount of activation energy of a [1,3] antarafacial shift transition state.8 páginasapplication/pdfspaUniverisdad de Los AndesVenezuelahttps://www.scopus.com/record/display.uri?eid=2-s2.0-85050232002&origin=inward&txGid=13e22fa7ea6a7cb64090d68001afaa07Estudio computacional del rearreglo sigmatrópico [1,3] de la (Z)-3-(4-(dimetilamino)bencilidén)tiocroman-4-onaComputational study of [1,3] sigmatropic rearrangement of the (Z)-3-(4-(dimethylamino)benzyliden)thiocroman-4- oneArtículo de revistahttp://purl.org/coar/resource_type/c_2df8fbb1Textinfo:eu-repo/semantics/articlehttp://purl.org/redcol/resource_type/ARTinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/version/c_970fb48d4fbd8a85Avances en Quimica1. P Böhler, Ch Tamm. The homo-isoflavones, a new class of natural product. Isolation and structure of eucomin and eucomol. Tetrahedron Letters, 8, 3479-3483 (1967).2. RE Finckh, Ch Tamm. The homo-isoflavones III. Isolation and structure of punctatin, 3,9-Dihydro-Punctatin, 4’-O-Methyl-3,9- dihydro-punctatin, 4’-Demethyl-eucomin and 4’-Demethyl-5-Omethyl-3,9-dihydro-eucomin. Experientia, 26, 472-473 (1970).3. TM Hung, CV Thu, NT Dat, SW Ryoo, JH Lee, JC Kim, M Na, HJ Jung, K Bae, BS Min. Homoisoflavonoid derivatives from the roots of Ophiopogon japonicus and their in vitro antiinflammation activity. Bioorganic & Medicinal Chemistry Letters, 20, 2412-2416 (2010).4. P Perjési, U Das, ED Clercq, J Balzarini, M Kawase, H Sakagami, JP Stables, T Lorand, Z Rozmer, JR Dimmock. Design, synthesis and antiproliferative activity of some 3- benzylidene-2,3-dihydro-1-benzopyran-4-ones which display selective toxicity for malignant cells. Eur. J. Medicinal Chemistry, 43, 839-845 (2008).5. T Al Nakib, V Bezjak, MJ Meegan, R Chandy. Synthesis and antifungal activity of some 3-benzylidenechroman-4-ones, 3- benzylidenethiochroman-4-ones and 2-benzylidene-1-tetralones. Eur. J. Medicinal Chemistry, 25, 455-462 (1990).6. YF Li, ZQ Liu, XY Luo. Properties of synthetic homoisoflavonoids to reduce oxidants and to protect linoleic acid and DNA against oxidation. Journal of Agricultural and Food Chemistry, 58, 4126-4131 (2010).7. S Tait, AL Salvati, N Desideri, L Fiore. Antiviral activity of substituted homoisoflavonoids on enteroviruses. Antiviral Research, 72, 252-255 (2006).8. AT Nguyen, J Fontaine, H Malonne, P Duez. Homoisoflavanones from Disporopsis aspera. Phytochemistry, 67, 2159-2163 (2006).9. T Ishikawa, Y Oku, T Tanaka, T Kumamoto. An approach to Anti-HIV-1 active Calophyllum Coumarin synthesis: An enantioselective construction of 2,3-Dimethyl-4-chromanone ring by Quinine-assisted intramolecular Michael-type addition. Tetrahedron Letters, 40, 3777-3780 (1999).10. A Lévai, Z Dinya, JB Schág, G Tóth, Á Szöllösy. Synthesis of 3-Benzyl-4-chromones and 3-Benzyl-1-thio-4-chromones. Pharmazie, 36, 465-466 (1981).11. J Andrieux, DRH Barton, H Patin. Rhodium-catalysed isomerisation of some unsaturated organic substrates. J. Chem. Soc., Perkin Transactions 1, 4, 359-363 (1977).12. J McMurry. Química Orgánica. Sexta Edición. Thomson (2004).13. RB Woodward, R Hoffmann. Selection rules for sigmatro picreactions. J. Amer. Chem. Soc., 87, 2511-2513 (1965).14. GB Gill. The application of the Woodward-Hoffman Orbital symmetry rules to concerted organic reactions. Quarterly Reviews Chemical Society, 22, 338-389 (1968).15. WR Rodwell, WJ Bouma, L Radom. Ab inition studies of 1,3- sigmatropic rearrangements: Effect of basis set and electron correlation. Int. J. Quantum Chemistry, 18, 107-116 (1980).16. Jr B A Hess, LJ Schaad, J Pancir. Theoretical Studies of [1,n]- sigmatropic rearrangements involving hydrogen transfer in simple methyl-substituted conjugated polyenes. J. Amer. Chem. Soc., 107, 149-154 (1985).17. LR Domingo, M.J. Aurell, P. Pérez. Understanding the Polar Mechanism of the Ene Reaction. A DFT Study. Org. Biomol. Chem., 12, 7581-7590 (2014)18. LR Domingo. Why Diels-Alder reactions are non-concerted processes. J. Chil. Chem. Soc., 59, 2615-2518 (2014)19. LR Domingo, MJ Aurell, P Pérez. The mechanism of ionic Diels-Alder reactions. A DFT study of the oxa-Povarov reaction. RSC Adv., 4, 16567-16577 (2014).20. D Yepes, JS Murray, P Pérez, LR Domingo, P Politzer, P Jaque. Complementarity of reaction force and electron localization function analyses of asynchronicity in bond formation in DielsAlder reactions. Phys. Chem. Chem. Phys., 16, 6726-6734 (2014).21. LR Domingo. State of the Art of the Bonding Changes along the Diels-Alder Reaction between Butadiene and Ethylene. Refuting the Pericyclic Mechanism. Organic Chemistry: Current Research, 2, 120 (2013).22. A Valkonen, K Laihia, E Kolehmainen, R Kauppinen, P Perjési. Structural studies of seven homoisoflavonoids, six thiohomoisoflavonoids, and four structurally related compounds. Structural Chemistry, 23, 209-217 (2012).23. Gaussian 09W, Revision A.02, Gaussian, Inc., Pittsburgh PA, (2009).24. E Márquez, J Mora, T Cordoba, G Chuchani. Theoretical Study of the Mechanism for the Gas-Phase Pyrolysis Kinetics of 2- Methylbenzyl Chloride. Int. J. Chemical Kinetics, 3, 537-546 (2011).25. E Marquez, T Cordova, G Chuchani. DFT Study of the GasPhase Thermal Decomposition Kinetics of 2-Ethoxypyridine into 2-Pyridone. Int. J. Quantum Chemistry, 112, 724–730 (2012)26. K Fukui. Formulation of the reaction coordinate. J. Physical Chemistry, 74, 4161-4163 (1970).27. JP Foster, F Weinhold. Natural hybrid orbitals. J. Amer. Chem. Soc., 102, 7211-7218 (1980).28. KB Wiberg. Application of the pople-santry-segal CNDO method to the cyclopropylcarbinyl and cyclobutyl cation and to bicyclobutane. Tetrahedron, 24, 1083-1096 (1968).29. A Moyano, MA Pericas, E Valenti. A theoretical study on the mechanism of the thermal and the acid-catalyzed descarboxylation of 2-Oxetanones (-Lactones). J. Org. Chem., 54, 573-582 (1989).30. O Francia. Síntesis y fotoquímica de tiocromonas para su posible uso en terapia fotodinámica antimicrobiana. Tesis de Licenciatura, Universidad Simón Bolívar, Sartenejas, Venezuela(2011).31. CE Hudson, D J McAdoo. An ab initio study of substituent effects in [1,3]-hydrogen shifts. J. Org. Chem., 68, 2735-2740 (2003).32. G Tóth, Å Szöllosy, A Lévai, G Oszbach, W Dietrich, H Kühne. Stereochemistry of 3-Arylideneflavanones and their thio analogues by the use of 3 J(CH) Couplings. Magnetic Resonance in Chemistry, 29, 801-804 (1991).33. F Bernardi, MA Robb, HB Schlegel, G Tonachini. An MC-SCF study of [1,3] and [1,2] sigmatropic shifts in propene. J. Amer. Chem. Soc., 106, 1198-1202 (1984)30232-3123-bencilidéntiocroman-4-onaRearreglo sigmatrópicoTFDEstado de transición3-Benzylidenethiochroman-4-oneSigmatropic rearrangementDFTTransition statePublicationORIGINALEstudio computacional del rearreglo sigmatrópico [1,3] de la.pdfEstudio computacional del rearreglo sigmatrópico [1,3] de la.pdfArtículoapplication/pdf583709https://repositorio.cuc.edu.co/bitstreams/fe27e347-042a-4956-b766-727559cbd639/downloadab157ffd8cda1adeeafb8064d7913479MD51LICENSElicense.txtlicense.txttext/plain; charset=utf-814828https://repositorio.cuc.edu.co/bitstreams/2d36f633-3049-4029-a498-e2332eabb5f4/download2f9959eaf5b71fae44bbf9ec84150c7aMD52TEXTEstudio computacional del rearreglo sigmatrópico [1,3] de la.pdf.txtEstudio computacional del rearreglo sigmatrópico [1,3] de la.pdf.txtExtracted texttext/plain32914https://repositorio.cuc.edu.co/bitstreams/4ba50ebc-ee55-44f5-bec8-716e3234d636/download99489f2f50cd3612c7478c97e50fcd67MD53THUMBNAILEstudio computacional del rearreglo sigmatrópico [1,3] de la.pdf.jpgEstudio computacional del rearreglo sigmatrópico [1,3] de la.pdf.jpgGenerated Thumbnailimage/jpeg16689https://repositorio.cuc.edu.co/bitstreams/6baeff36-6efb-4595-9b53-830e89cae4de/downloadd70512192c504b16858fac0034a030b0MD5411323/10741oai:repositorio.cuc.edu.co:11323/107412024-09-17 12:47:01.869https://creativecommons.org/licenses/by-nc-sa/4.0/© Copyright 2018 Elsevier B.V., All rights reserved.open.accesshttps://repositorio.cuc.edu.coRepositorio de la Universidad de la Costa CUCrepdigital@cuc.edu.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