Conformational sieving effect of organic structure-directing agents during the synthesis of zeolitic materials

In this work we find a novel conformational sieving effect during the structure-direction of two chiral organic diastereoisomers, (1R,2S)-benzyl-ephedrine and (1S,2S)-benzyl-pseudoephedrine, during the synthesis of zeolitic aluminophosphates. Protonation of each diastereoisomer can take place throug...

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Autores: Nieto-Hernández, David, Pérez-Pariente, Joaquín, Toran, Ennrique, López-Arbeloa, Fernando, Gómez-Hortigüela Sainz, Luis
Tipo de recurso: artículo
Estado:Versión aceptada para publicación
Fecha de publicación:2019
País:España
Institución:Consejo Superior de Investigaciones Científicas (CSIC)
Repositorio:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/191087
Acceso en línea:http://hdl.handle.net/10261/191087
Access Level:acceso abierto
Palabra clave:Template
Chirality
Zeolite
Aluminophosphates
Structure-directing agent
Diastereoselective
Conformers
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spelling Conformational sieving effect of organic structure-directing agents during the synthesis of zeolitic materialsNieto-Hernández, DavidPérez-Pariente, JoaquínToran, EnnriqueLópez-Arbeloa, FernandoGómez-Hortigüela Sainz, LuisTemplateChiralityZeoliteAluminophosphatesStructure-directing agentDiastereoselectiveConformersIn this work we find a novel conformational sieving effect during the structure-direction of two chiral organic diastereoisomers, (1R,2S)-benzyl-ephedrine and (1S,2S)-benzyl-pseudoephedrine, during the synthesis of zeolitic aluminophosphates. Protonation of each diastereoisomer can take place through two different stereochemical configurations, giving place to a new stereogenic N center that results in two stereoisomers for each molecule, with (1R,2S,NS) or (1R,2S,NR) configurations for benzyl-ephedrine or (1S,2S,NR) or (1S,2S,NS) configurations for benzyl-pseudoephedrine. Through a combination of H and C NMR spectroscopies and DFT + D computational calculations we are able to distinguish the two stereoisomers derived from benzyl-pseudoephedrine: results show a higher occurrence of the (1S,2S,NS) isomer in aqueous solution, displaying a folded molecular configuration, while the less abundant (1S,2S,NR) isomer displays instead a conformation with an elongated shape. Crystallization of microporous aluminophosphates in the presence of benzyl-pseudoephedrine results in materials with AFI structure based on one-dimensional channels with a surprising higher occurrence of the (1S,2S,NR) isomer, in sharp contrast with the behavior in aqueous solution. Such notable difference is ascribed to the elongated shape of the (1S,2S,NR) stereoisomer that can better fit within the AFI one-dimensional nano-channels. On the other hand, assignment of the H and C NMR bands to the different protonated stereoisomers of (1R,2S)-benzyl-ephedrine is not as clear due to the smaller splitting of the signals upon protonation through the two stereochemical configurations. This work demonstrates that confinement in nano-spaces can alter the relative stability of stereoisomers in open spaces, leading to the occurrence of species that would not be possible otherwise.This work has been partiallyfinanced by the Spanish State ResearchAgency (Agencia Española de Investigación, AEI) and the European Regional Development Fund (Fondo Europeo de Desarrollo Regional,FEDER) through the Project MAT2016-77496-R (AEI/FEDER, UE), andby Consejo Superior de Investigaciones Científicas (CSIC) through project 201780I043. DN acknowledges the Youth Employment Initiative and European Social Fund and Comunidad Autónoma de Madrid for funding his contract (PEJD-2017-PRE/IND-3801). Secretaría General Adjunta de Informática-CSIC is acknowledged for running thecalculations, and BIOVIA for providing the computational software;Peer ReviewedElsevierMinisterio de Economía y Competitividad (España)Consejo Superior de Investigaciones Científicas (España)Comunidad de MadridConsejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]2019201920192019info:eu-repo/semantics/articlehttp://purl.org/coar/resource_type/c_6501Postprintinfo:eu-repo/semantics/acceptedVersionhttp://hdl.handle.net/10261/191087reponame:DIGITAL.CSIC. Repositorio Institucional del CSICinstname:Consejo Superior de Investigaciones Científicas (CSIC)Inglés#PLACEHOLDER_PARENT_METADATA_VALUE#info:eu-repo/grantAgreement/MINECO/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/MAT2016-77496-Rhttps://doi.org/10.1016/j.micromeso.2019.05.052Síinfo:eu-repo/semantics/openAccessoai:digital.csic.es:10261/1910872026-05-22T06:33:51Z
dc.title.none.fl_str_mv Conformational sieving effect of organic structure-directing agents during the synthesis of zeolitic materials
title Conformational sieving effect of organic structure-directing agents during the synthesis of zeolitic materials
spellingShingle Conformational sieving effect of organic structure-directing agents during the synthesis of zeolitic materials
Nieto-Hernández, David
Template
Chirality
Zeolite
Aluminophosphates
Structure-directing agent
Diastereoselective
Conformers
title_short Conformational sieving effect of organic structure-directing agents during the synthesis of zeolitic materials
title_full Conformational sieving effect of organic structure-directing agents during the synthesis of zeolitic materials
title_fullStr Conformational sieving effect of organic structure-directing agents during the synthesis of zeolitic materials
title_full_unstemmed Conformational sieving effect of organic structure-directing agents during the synthesis of zeolitic materials
title_sort Conformational sieving effect of organic structure-directing agents during the synthesis of zeolitic materials
dc.creator.none.fl_str_mv Nieto-Hernández, David
Pérez-Pariente, Joaquín
Toran, Ennrique
López-Arbeloa, Fernando
Gómez-Hortigüela Sainz, Luis
author Nieto-Hernández, David
author_facet Nieto-Hernández, David
Pérez-Pariente, Joaquín
Toran, Ennrique
López-Arbeloa, Fernando
Gómez-Hortigüela Sainz, Luis
author_role author
author2 Pérez-Pariente, Joaquín
Toran, Ennrique
López-Arbeloa, Fernando
Gómez-Hortigüela Sainz, Luis
author2_role author
author
author
author
dc.contributor.none.fl_str_mv Ministerio de Economía y Competitividad (España)
Consejo Superior de Investigaciones Científicas (España)
Comunidad de Madrid
Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]
dc.subject.none.fl_str_mv Template
Chirality
Zeolite
Aluminophosphates
Structure-directing agent
Diastereoselective
Conformers
topic Template
Chirality
Zeolite
Aluminophosphates
Structure-directing agent
Diastereoselective
Conformers
description In this work we find a novel conformational sieving effect during the structure-direction of two chiral organic diastereoisomers, (1R,2S)-benzyl-ephedrine and (1S,2S)-benzyl-pseudoephedrine, during the synthesis of zeolitic aluminophosphates. Protonation of each diastereoisomer can take place through two different stereochemical configurations, giving place to a new stereogenic N center that results in two stereoisomers for each molecule, with (1R,2S,NS) or (1R,2S,NR) configurations for benzyl-ephedrine or (1S,2S,NR) or (1S,2S,NS) configurations for benzyl-pseudoephedrine. Through a combination of H and C NMR spectroscopies and DFT + D computational calculations we are able to distinguish the two stereoisomers derived from benzyl-pseudoephedrine: results show a higher occurrence of the (1S,2S,NS) isomer in aqueous solution, displaying a folded molecular configuration, while the less abundant (1S,2S,NR) isomer displays instead a conformation with an elongated shape. Crystallization of microporous aluminophosphates in the presence of benzyl-pseudoephedrine results in materials with AFI structure based on one-dimensional channels with a surprising higher occurrence of the (1S,2S,NR) isomer, in sharp contrast with the behavior in aqueous solution. Such notable difference is ascribed to the elongated shape of the (1S,2S,NR) stereoisomer that can better fit within the AFI one-dimensional nano-channels. On the other hand, assignment of the H and C NMR bands to the different protonated stereoisomers of (1R,2S)-benzyl-ephedrine is not as clear due to the smaller splitting of the signals upon protonation through the two stereochemical configurations. This work demonstrates that confinement in nano-spaces can alter the relative stability of stereoisomers in open spaces, leading to the occurrence of species that would not be possible otherwise.
publishDate 2019
dc.date.none.fl_str_mv 2019
2019
2019
2019
dc.type.none.fl_str_mv info:eu-repo/semantics/article
http://purl.org/coar/resource_type/c_6501
Postprint
info:eu-repo/semantics/acceptedVersion
format article
status_str acceptedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/10261/191087
url http://hdl.handle.net/10261/191087
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv #PLACEHOLDER_PARENT_METADATA_VALUE#
info:eu-repo/grantAgreement/MINECO/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/MAT2016-77496-R
https://doi.org/10.1016/j.micromeso.2019.05.052
Sí
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.publisher.none.fl_str_mv Elsevier
publisher.none.fl_str_mv Elsevier
dc.source.none.fl_str_mv reponame:DIGITAL.CSIC. Repositorio Institucional del CSIC
instname:Consejo Superior de Investigaciones Científicas (CSIC)
instname_str Consejo Superior de Investigaciones Científicas (CSIC)
reponame_str DIGITAL.CSIC. Repositorio Institucional del CSIC
collection DIGITAL.CSIC. Repositorio Institucional del CSIC
repository.name.fl_str_mv
repository.mail.fl_str_mv
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