Uncovering the mechanism leading to the synthesis of symmetric and asymmetric Tröger's bases

Autores
Lanza, Priscila Ailín; Dusso, Diego; Ramirez, Cristina Lujan; Parise, Alejandro Ruben; Chesta, Carlos Alberto; Moyano, Elizabeth Laura; Vera, Domingo Mariano Adolfo
Año de publicación
2019
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Tröger´s bases have been attracting great interest due to their potential applications in nanoelectronics, supramolecular chemistry, molecular recognition, biological activity and auxiliaries for asymmetric synthesis. However, a detailed step by step proposal for the mechanism leading to the production of these compounds is still uncovered. A set of five model syntheses of symmetric and asymmetric Tröger´s base derivatives starting from substituted anilines and formaldehyde was done and envisaged as representative for understanding the underlying mechanism. All reasonable pathways were thoroughly scanned by means of DFT calculations. The highest energy TS was associated with the entrance of the first formaldehyde which produces the first out of three key carbocations. The last step, the closure of the methylene-bridged diazocyne heterocycle was also found of kinetic relevance and as a source of stable intermediates or byproducts. The whole mechanistic picture would provide keys for the rational planning of the synthesis of these compounds.
Fil: Lanza, Priscila Ailín. Universidad Nacional de Mar del Plata; Argentina. Consejo Nacional de Investigaciones Cientificas y Tecnicas. Centro Cientifico Tecnologico Conicet - Mar del Plata. Instituto de Investigaciones En Biodiversidad y Biotecnologia. Grupo de Investigacion En Quimica Analitica y Modelado Molecular.; Argentina
Fil: Dusso, Diego. Departamento de Química; Argentina
Fil: Ramirez, Cristina Lujan. Universidad Nacional de Mar del Plata; Argentina
Fil: Parise, Alejandro Ruben. Consejo Nacional de Investigaciones Cientificas y Tecnicas. Centro Cientifico Tecnologico Conicet - Mar del Plata. Instituto de Investigaciones En Biodiversidad y Biotecnologia. Grupo de Investigacion En Quimica Analitica y Modelado Molecular.; Argentina. Universidad Nacional de Mar del Plata; Argentina
Fil: Chesta, Carlos Alberto. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina
Fil: Moyano, Elizabeth Laura. Universidad Nacional de Córdoba. Facultad de Ciencias Exactas, Físicas y Naturales; Argentina
Fil: Vera, Domingo Mariano Adolfo. Universidad Nacional de Mar del Plata; Argentina. Consejo Nacional de Investigaciones Cientificas y Tecnicas. Centro Cientifico Tecnologico Conicet - Mar del Plata. Instituto de Investigaciones En Biodiversidad y Biotecnologia. Grupo de Investigacion En Quimica Analitica y Modelado Molecular.; Argentina
Materia
bases de troger
mecanismo
DFT
sustituyentes
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/117616
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/117616
network_acronym_str CONICETDig
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network_name_str CONICET Digital (CONICET)
spelling Uncovering the mechanism leading to the synthesis of symmetric and asymmetric Tröger's basesLanza, Priscila AilínDusso, DiegoRamirez, Cristina LujanParise, Alejandro RubenChesta, Carlos AlbertoMoyano, Elizabeth LauraVera, Domingo Mariano Adolfobases de trogermecanismoDFTsustituyenteshttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1Tröger´s bases have been attracting great interest due to their potential applications in nanoelectronics, supramolecular chemistry, molecular recognition, biological activity and auxiliaries for asymmetric synthesis. However, a detailed step by step proposal for the mechanism leading to the production of these compounds is still uncovered. A set of five model syntheses of symmetric and asymmetric Tröger´s base derivatives starting from substituted anilines and formaldehyde was done and envisaged as representative for understanding the underlying mechanism. All reasonable pathways were thoroughly scanned by means of DFT calculations. The highest energy TS was associated with the entrance of the first formaldehyde which produces the first out of three key carbocations. The last step, the closure of the methylene-bridged diazocyne heterocycle was also found of kinetic relevance and as a source of stable intermediates or byproducts. The whole mechanistic picture would provide keys for the rational planning of the synthesis of these compounds.Fil: Lanza, Priscila Ailín. Universidad Nacional de Mar del Plata; Argentina. Consejo Nacional de Investigaciones Cientificas y Tecnicas. Centro Cientifico Tecnologico Conicet - Mar del Plata. Instituto de Investigaciones En Biodiversidad y Biotecnologia. Grupo de Investigacion En Quimica Analitica y Modelado Molecular.; ArgentinaFil: Dusso, Diego. Departamento de Química; ArgentinaFil: Ramirez, Cristina Lujan. Universidad Nacional de Mar del Plata; ArgentinaFil: Parise, Alejandro Ruben. Consejo Nacional de Investigaciones Cientificas y Tecnicas. Centro Cientifico Tecnologico Conicet - Mar del Plata. Instituto de Investigaciones En Biodiversidad y Biotecnologia. Grupo de Investigacion En Quimica Analitica y Modelado Molecular.; Argentina. Universidad Nacional de Mar del Plata; ArgentinaFil: Chesta, Carlos Alberto. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; ArgentinaFil: Moyano, Elizabeth Laura. Universidad Nacional de Córdoba. Facultad de Ciencias Exactas, Físicas y Naturales; ArgentinaFil: Vera, Domingo Mariano Adolfo. Universidad Nacional de Mar del Plata; Argentina. Consejo Nacional de Investigaciones Cientificas y Tecnicas. Centro Cientifico Tecnologico Conicet - Mar del Plata. Instituto de Investigaciones En Biodiversidad y Biotecnologia. Grupo de Investigacion En Quimica Analitica y Modelado Molecular.; ArgentinaWiley VCH Verlag2019-11info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/117616Lanza, Priscila Ailín; Dusso, Diego; Ramirez, Cristina Lujan; Parise, Alejandro Ruben; Chesta, Carlos Alberto; et al.; Uncovering the mechanism leading to the synthesis of symmetric and asymmetric Tröger's bases; Wiley VCH Verlag; European Journal of Organic Chemistry; 2019; 47; 11-2019; 7644-76551434-193XCONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://chemistry-europe.onlinelibrary.wiley.com/doi/abs/10.1002/ejoc.201901141info:eu-repo/semantics/altIdentifier/doi/10.1002/ejoc.201901141info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T10:07:41Zoai:ri.conicet.gov.ar:11336/117616instacron:CONICETInstitucionalhttp://ri.conicet.gov.ar/Organismo científico-tecnológicoNo correspondehttp://ri.conicet.gov.ar/oai/requestdasensio@conicet.gov.ar; lcarlino@conicet.gov.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:34982025-09-29 10:07:41.723CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Uncovering the mechanism leading to the synthesis of symmetric and asymmetric Tröger's bases
title Uncovering the mechanism leading to the synthesis of symmetric and asymmetric Tröger's bases
spellingShingle Uncovering the mechanism leading to the synthesis of symmetric and asymmetric Tröger's bases
Lanza, Priscila Ailín
bases de troger
mecanismo
DFT
sustituyentes
title_short Uncovering the mechanism leading to the synthesis of symmetric and asymmetric Tröger's bases
title_full Uncovering the mechanism leading to the synthesis of symmetric and asymmetric Tröger's bases
title_fullStr Uncovering the mechanism leading to the synthesis of symmetric and asymmetric Tröger's bases
title_full_unstemmed Uncovering the mechanism leading to the synthesis of symmetric and asymmetric Tröger's bases
title_sort Uncovering the mechanism leading to the synthesis of symmetric and asymmetric Tröger's bases
dc.creator.none.fl_str_mv Lanza, Priscila Ailín
Dusso, Diego
Ramirez, Cristina Lujan
Parise, Alejandro Ruben
Chesta, Carlos Alberto
Moyano, Elizabeth Laura
Vera, Domingo Mariano Adolfo
author Lanza, Priscila Ailín
author_facet Lanza, Priscila Ailín
Dusso, Diego
Ramirez, Cristina Lujan
Parise, Alejandro Ruben
Chesta, Carlos Alberto
Moyano, Elizabeth Laura
Vera, Domingo Mariano Adolfo
author_role author
author2 Dusso, Diego
Ramirez, Cristina Lujan
Parise, Alejandro Ruben
Chesta, Carlos Alberto
Moyano, Elizabeth Laura
Vera, Domingo Mariano Adolfo
author2_role author
author
author
author
author
author
dc.subject.none.fl_str_mv bases de troger
mecanismo
DFT
sustituyentes
topic bases de troger
mecanismo
DFT
sustituyentes
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv Tröger´s bases have been attracting great interest due to their potential applications in nanoelectronics, supramolecular chemistry, molecular recognition, biological activity and auxiliaries for asymmetric synthesis. However, a detailed step by step proposal for the mechanism leading to the production of these compounds is still uncovered. A set of five model syntheses of symmetric and asymmetric Tröger´s base derivatives starting from substituted anilines and formaldehyde was done and envisaged as representative for understanding the underlying mechanism. All reasonable pathways were thoroughly scanned by means of DFT calculations. The highest energy TS was associated with the entrance of the first formaldehyde which produces the first out of three key carbocations. The last step, the closure of the methylene-bridged diazocyne heterocycle was also found of kinetic relevance and as a source of stable intermediates or byproducts. The whole mechanistic picture would provide keys for the rational planning of the synthesis of these compounds.
Fil: Lanza, Priscila Ailín. Universidad Nacional de Mar del Plata; Argentina. Consejo Nacional de Investigaciones Cientificas y Tecnicas. Centro Cientifico Tecnologico Conicet - Mar del Plata. Instituto de Investigaciones En Biodiversidad y Biotecnologia. Grupo de Investigacion En Quimica Analitica y Modelado Molecular.; Argentina
Fil: Dusso, Diego. Departamento de Química; Argentina
Fil: Ramirez, Cristina Lujan. Universidad Nacional de Mar del Plata; Argentina
Fil: Parise, Alejandro Ruben. Consejo Nacional de Investigaciones Cientificas y Tecnicas. Centro Cientifico Tecnologico Conicet - Mar del Plata. Instituto de Investigaciones En Biodiversidad y Biotecnologia. Grupo de Investigacion En Quimica Analitica y Modelado Molecular.; Argentina. Universidad Nacional de Mar del Plata; Argentina
Fil: Chesta, Carlos Alberto. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina
Fil: Moyano, Elizabeth Laura. Universidad Nacional de Córdoba. Facultad de Ciencias Exactas, Físicas y Naturales; Argentina
Fil: Vera, Domingo Mariano Adolfo. Universidad Nacional de Mar del Plata; Argentina. Consejo Nacional de Investigaciones Cientificas y Tecnicas. Centro Cientifico Tecnologico Conicet - Mar del Plata. Instituto de Investigaciones En Biodiversidad y Biotecnologia. Grupo de Investigacion En Quimica Analitica y Modelado Molecular.; Argentina
description Tröger´s bases have been attracting great interest due to their potential applications in nanoelectronics, supramolecular chemistry, molecular recognition, biological activity and auxiliaries for asymmetric synthesis. However, a detailed step by step proposal for the mechanism leading to the production of these compounds is still uncovered. A set of five model syntheses of symmetric and asymmetric Tröger´s base derivatives starting from substituted anilines and formaldehyde was done and envisaged as representative for understanding the underlying mechanism. All reasonable pathways were thoroughly scanned by means of DFT calculations. The highest energy TS was associated with the entrance of the first formaldehyde which produces the first out of three key carbocations. The last step, the closure of the methylene-bridged diazocyne heterocycle was also found of kinetic relevance and as a source of stable intermediates or byproducts. The whole mechanistic picture would provide keys for the rational planning of the synthesis of these compounds.
publishDate 2019
dc.date.none.fl_str_mv 2019-11
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
http://purl.org/coar/resource_type/c_6501
info:ar-repo/semantics/articulo
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/11336/117616
Lanza, Priscila Ailín; Dusso, Diego; Ramirez, Cristina Lujan; Parise, Alejandro Ruben; Chesta, Carlos Alberto; et al.; Uncovering the mechanism leading to the synthesis of symmetric and asymmetric Tröger's bases; Wiley VCH Verlag; European Journal of Organic Chemistry; 2019; 47; 11-2019; 7644-7655
1434-193X
CONICET Digital
CONICET
url http://hdl.handle.net/11336/117616
identifier_str_mv Lanza, Priscila Ailín; Dusso, Diego; Ramirez, Cristina Lujan; Parise, Alejandro Ruben; Chesta, Carlos Alberto; et al.; Uncovering the mechanism leading to the synthesis of symmetric and asymmetric Tröger's bases; Wiley VCH Verlag; European Journal of Organic Chemistry; 2019; 47; 11-2019; 7644-7655
1434-193X
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/https://chemistry-europe.onlinelibrary.wiley.com/doi/abs/10.1002/ejoc.201901141
info:eu-repo/semantics/altIdentifier/doi/10.1002/ejoc.201901141
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
application/pdf
application/pdf
dc.publisher.none.fl_str_mv Wiley VCH Verlag
publisher.none.fl_str_mv Wiley VCH Verlag
dc.source.none.fl_str_mv reponame:CONICET Digital (CONICET)
instname:Consejo Nacional de Investigaciones Científicas y Técnicas
reponame_str CONICET Digital (CONICET)
collection CONICET Digital (CONICET)
instname_str Consejo Nacional de Investigaciones Científicas y Técnicas
repository.name.fl_str_mv CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicas
repository.mail.fl_str_mv dasensio@conicet.gov.ar; lcarlino@conicet.gov.ar
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score 13.070432

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