Autocondensación de Aldehídos α, β-insaturados Organocatalizado por Carbenos N-Heterocíclico

ilustraciones, diagramas, fotografías

Autores:
Morales Manrique, Oscar Camilo
Tipo de recurso:
Fecha de publicación:
2023
Institución:
Universidad Nacional de Colombia
Repositorio:
Universidad Nacional de Colombia
Idioma:
spa
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oai:repositorio.unal.edu.co:unal/84255
Acceso en línea:
https://repositorio.unal.edu.co/handle/unal/84255
https://repositorio.unal.edu.co/
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540 - Química y ciencias afines::547 - Química orgánica
540 - Química y ciencias afines::542 - Técnicas, procedimientos, aparatos, equipos, materiales
Catalizadores
Procesos de manufacturación
Condesación
Catalysts
Manufacturing processes
Condensation
Carbenos N-heterocíclico
Auto condensación
Aldehídos alfa, beta insaturados
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openAccess
License
Atribución-NoComercial-SinDerivadas 4.0 Internacional
id UNACIONAL2_b4ee9e96bce220b97771e7aeb24a521d
oai_identifier_str oai:repositorio.unal.edu.co:unal/84255
network_acronym_str UNACIONAL2
network_name_str Universidad Nacional de Colombia
repository_id_str
dc.title.spa.fl_str_mv Autocondensación de Aldehídos α, β-insaturados Organocatalizado por Carbenos N-Heterocíclico
dc.title.translated.eng.fl_str_mv Self-Condensation Of α, β -Unsaturated Aldehydes Organocatalyzed By N-Heterocyclic Carbenes
title Autocondensación de Aldehídos α, β-insaturados Organocatalizado por Carbenos N-Heterocíclico
spellingShingle Autocondensación de Aldehídos α, β-insaturados Organocatalizado por Carbenos N-Heterocíclico
540 - Química y ciencias afines::547 - Química orgánica
540 - Química y ciencias afines::542 - Técnicas, procedimientos, aparatos, equipos, materiales
Catalizadores
Procesos de manufacturación
Condesación
Catalysts
Manufacturing processes
Condensation
Carbenos N-heterocíclico
Auto condensación
Aldehídos alfa, beta insaturados
title_short Autocondensación de Aldehídos α, β-insaturados Organocatalizado por Carbenos N-Heterocíclico
title_full Autocondensación de Aldehídos α, β-insaturados Organocatalizado por Carbenos N-Heterocíclico
title_fullStr Autocondensación de Aldehídos α, β-insaturados Organocatalizado por Carbenos N-Heterocíclico
title_full_unstemmed Autocondensación de Aldehídos α, β-insaturados Organocatalizado por Carbenos N-Heterocíclico
title_sort Autocondensación de Aldehídos α, β-insaturados Organocatalizado por Carbenos N-Heterocíclico
dc.creator.fl_str_mv Morales Manrique, Oscar Camilo
dc.contributor.advisor.none.fl_str_mv Baquero Velasco, Edwin Arley
Guevara Pulido, James Oswaldo
dc.contributor.author.none.fl_str_mv Morales Manrique, Oscar Camilo
dc.contributor.researchgroup.spa.fl_str_mv Estado Sólido y Catálisis Ambiental
dc.contributor.orcid.spa.fl_str_mv 0009-0000-2677-7959
dc.contributor.cvlac.spa.fl_str_mv Morales Manrique, Oscar
dc.contributor.researchgate.spa.fl_str_mv Camilo Morales-Manrique
dc.subject.ddc.spa.fl_str_mv 540 - Química y ciencias afines::547 - Química orgánica
540 - Química y ciencias afines::542 - Técnicas, procedimientos, aparatos, equipos, materiales
topic 540 - Química y ciencias afines::547 - Química orgánica
540 - Química y ciencias afines::542 - Técnicas, procedimientos, aparatos, equipos, materiales
Catalizadores
Procesos de manufacturación
Condesación
Catalysts
Manufacturing processes
Condensation
Carbenos N-heterocíclico
Auto condensación
Aldehídos alfa, beta insaturados
dc.subject.lemb.spa.fl_str_mv Catalizadores
Procesos de manufacturación
Condesación
dc.subject.lemb.eng.fl_str_mv Catalysts
Manufacturing processes
Condensation
dc.subject.proposal.spa.fl_str_mv Carbenos N-heterocíclico
Auto condensación
Aldehídos alfa, beta insaturados
description ilustraciones, diagramas, fotografías
publishDate 2023
dc.date.accessioned.none.fl_str_mv 2023-07-24T21:26:06Z
dc.date.available.none.fl_str_mv 2023-07-24T21:26:06Z
dc.date.issued.none.fl_str_mv 2023
dc.type.spa.fl_str_mv Trabajo de grado - Maestría
dc.type.driver.spa.fl_str_mv info:eu-repo/semantics/masterThesis
dc.type.version.spa.fl_str_mv info:eu-repo/semantics/acceptedVersion
dc.type.content.spa.fl_str_mv Text
dc.type.redcol.spa.fl_str_mv http://purl.org/redcol/resource_type/TM
status_str acceptedVersion
dc.identifier.uri.none.fl_str_mv https://repositorio.unal.edu.co/handle/unal/84255
dc.identifier.instname.spa.fl_str_mv Universidad Nacional de Colombia
dc.identifier.reponame.spa.fl_str_mv Repositorio Institucional Universidad Nacional de Colombia
dc.identifier.repourl.spa.fl_str_mv https://repositorio.unal.edu.co/
url https://repositorio.unal.edu.co/handle/unal/84255
https://repositorio.unal.edu.co/
identifier_str_mv Universidad Nacional de Colombia
Repositorio Institucional Universidad Nacional de Colombia
dc.language.iso.spa.fl_str_mv spa
language spa
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spelling Atribución-NoComercial-SinDerivadas 4.0 Internacionalhttp://creativecommons.org/licenses/by-nc-nd/4.0/info:eu-repo/semantics/openAccesshttp://purl.org/coar/access_right/c_abf2Baquero Velasco, Edwin Arleya0215cba2df4047cc9177f789693255bGuevara Pulido, James Oswaldo61f0d165cf1621d5e0a1caf2e7b10c26Morales Manrique, Oscar Camilod8df380cdf4e37c9a8c16d0aaefe1832Estado Sólido y Catálisis Ambiental0009-0000-2677-7959Morales Manrique, OscarCamilo Morales-Manrique2023-07-24T21:26:06Z2023-07-24T21:26:06Z2023https://repositorio.unal.edu.co/handle/unal/84255Universidad Nacional de ColombiaRepositorio Institucional Universidad Nacional de Colombiahttps://repositorio.unal.edu.co/ilustraciones, diagramas, fotografíasLos carbenos N-heterocíclicos (NHCs) son moléculas que suelen emplearse junto a metales de transición como catalizadores organometálicos. A pesar de sus grandes virtudes como catalizadores, los complejos organometálicos suelen ser rechazados en muchos procesos industriales debido a la presencia de trazas de metales pesados en los productos finales y la dificultad de su eliminación. Es por esta razón que desde hace algunos años los NHCs han sido objeto de estudios que buscan su implementación como organocatalizadores. Estos procesos han demostrado ser menos selectivos que sus competidores organometálicos. Sin embargo, el fácil acceso a estos catalizadores (muchos se extraen de fuentes naturales o se sintetizan de una manera sencilla) hace que los procesos sean menos costosos y por supuesto, menos tóxicos porque se evita la presencia de metales. Tanto así que, en el último tiempo, múltiples reacciones que involucraban procesos organometálicos, han sido ensayados en presencia de organocatalizadores encontrando rendimientos, relaciones diastereoméricas y excesos enantioméricos favorables. Este último aspecto es fundamental en la síntesis total y en la química medicinal, pues muchos compuestos empleados como fármacos suelen ser ópticamente activos y administrados en muchos casos en sus formas enantioméricamente puras por lo que desarrollar procesos catalíticos enantioselectivos resulta muy atractivo para estas dos áreas. En este sentido, nosotros presentamos aquí el empleo de NHCs como activadores de aldehídos α, β insaturados a partir de adiciones 1,2. Nosotros encontramos que posterior a dicha adición los aldehídos experimentan transformaciones electrónicas que varían el comportamiento electrofílico/nucleofílico típico de sus diversas posiciones y que, dadas estas circunstancias no es necesario agregar compuestos adicionales para que estos interaccionen, generando reacciones de autocondensación del aldehído inicial a través de la formación de enlaces C-C y C-O. De esta forma y empleando cinamaldehído, crotonaldehído y furfural, tres compuestos sencillos y económicos, se lograron obtener γ-butirolactonas (moléculas bloques de construcción de muchos compuestos con actividad biológica) y α-hidroxicetonas (moléculas muy reactivas que suelen ser útiles en química orgánica como precursores). En el caso de la reacción con cinamaldehído, se pudo obtener buenas relaciones diastereoméricas (86:14 cis:trans) y un exceso enantiomérico resaltable (70% en el producto mayoritario, cis) cuando se evaluó un organocatalizador quiral. Adicionalmente, en la reacción con cinamaldehído, se buscó dar una explicación a la reactividad mostrada por esta molécula a partir de un estudio computacional basado en cálculos DFT que permitió esbozar su mecanismo de reacción y entender los requerimientos energéticos que este proceso demanda. Mediante estos cálculos se encontró también el doble rol de la base empleada (Cs2CO3) en la reacción ya que además de deprotonar la sal de imidazolio para generar la especie catalíticamente activa, ayuda el proceso de transferencia de protón de uno de los intermediarios disminuyendo la energía del proceso en 27.7 kcal/mol comparado a una transferencia típica de protón intramolecular. (Texto tomado de la fuente)N-heterocyclic carbenes (NHCs) are molecules that are often used together with transition metals as organometallic catalysts. Despite their great performances as catalysts, organometallic complexes are often rejected in many industrial processes due to the presence of traces of heavy metals in the final products and the difficulty of their removal. This is why since some years ago, NHCs have been studied as organocatalysts. These processes have proven to be less selective than their organometallic analogs. However, the easy access to these catalysts (many are extracted from natural sources or synthesized in a simple way) makes the processes less expensive and, of course, less toxic because the presence of metals is avoided. Thus, multiple reactions involving organometallic processes have been tested in the presence of organocatalysts, finding favorable yields, diastereomeric ratios and enantiomeric excesses. The latter is fundamental in total synthesis and medicinal chemistry, since many compounds used as drugs are usually optically active and administered in many cases in their enantiomerically pure forms, making the development of enantioselective catalytic processes very attractive for these two areas. In this regard, we present here the use of NHCs as activators of α, β-unsaturated aldehydes from 1,2-additions. We find that after such addition the aldehydes undergo electronic transformations that vary the typical electrophilic/nucleophilic behavior of their various positions and that, given these circumstances, it is not necessary to add additional compounds for them to interact, generating self-condensation reactions of the initial aldehyde through the formation of C-C and C-O bonds. In this way, by using cinnamaldehyde, crotonaldehyde, and furfural, three simple and cheap compounds, it was possible to obtain γ-butyrolactones (building block molecules of many compounds with biological activity) and α-hydroxyketones (very reactive molecules that are usually useful in organic chemistry as precursors). Regarding the condensation of cinnamaldehyde, it was possible to obtain a good diastereomeric ratio (86:14 cis:trans) and a remarkable enantiomeric excess (70% of the major product, cis) when a chiral organocatalyst was tested in the reaction. Additionally, in the reaction with cinnamaldehyde, we tried to explain the reactivity shown by this compound from a computational study based on DFT calculations that allowed us to outline its reaction mechanism and understand the energetic requirements this process requires. By performing these calculations, we were able to uncover the dual role of the base used (Cs2CO3) in the reaction. It not only deprotonates the imidazolium salt to generate the catalytically active species, but it also facilitates the proton transfer process of one of the intermediates by reducing the energy required for the process by 27.7 kcal/mol compared to the common intramolecular proton transferMaestríaMagíster en Ciencias - QuímicaOrganocatálisis97 páginasapplication/pdfspaUniversidad Nacional de ColombiaBogotá - Ciencias - Maestría en Ciencias - QuímicaFacultad de CienciasBogotá,ColombiaUniversidad Nacional de Colombia - Sede Bogotá540 - Química y ciencias afines::547 - Química orgánica540 - Química y ciencias afines::542 - Técnicas, procedimientos, aparatos, equipos, materialesCatalizadoresProcesos de manufacturaciónCondesaciónCatalystsManufacturing processesCondensationCarbenos N-heterocíclicoAuto condensaciónAldehídos alfa, beta insaturadosAutocondensación de Aldehídos α, β-insaturados Organocatalizado por Carbenos N-HeterocíclicoSelf-Condensation Of α, β -Unsaturated Aldehydes Organocatalyzed By N-Heterocyclic CarbenesTrabajo de grado - Maestríainfo:eu-repo/semantics/masterThesisinfo:eu-repo/semantics/acceptedVersionTexthttp://purl.org/redcol/resource_type/TMBurstein, C. & Glorius, F. 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Soc. 131, 17995–17997 (2009).EstudiantesInvestigadoresMaestrosLICENSElicense.txtlicense.txttext/plain; charset=utf-85879https://repositorio.unal.edu.co/bitstream/unal/84255/1/license.txteb34b1cf90b7e1103fc9dfd26be24b4aMD51ORIGINAL1032487256.2023.pdf1032487256.2023.pdfTesis de Maestría en Ciencias - Químicaapplication/pdf2798260https://repositorio.unal.edu.co/bitstream/unal/84255/2/1032487256.2023.pdf5e113139f819a11c9d7851f3e9fa474aMD52unal/84255oai:repositorio.unal.edu.co:unal/842552023-07-24 16:30:07.515Repositorio Institucional Universidad Nacional de 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