Transient and intermediate carbocations in ruthenium tetroxide oxidation of saturated rings

The ruthenium tetroxide-mediated oxidation of cyclopentane, tetrahydrofuran, tetrahydrothiophene and N-substituted pyrrolidines has been studied computationally by DFT and topological (analysis of the electron localization function, ELF) methods. In agreement with experimental observations and previ...

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Authors: Pedrón, Manuel, Legnani, Laura, Chiacchio, Maria A., Caramella, Pierluigi, Tejero, Tomás, Merino, Pedro
Format: article
Status:Published version
Publication Date:2019
Country:España
Institution:Consejo Superior de Investigaciones Científicas (CSIC)
Repository:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/220637
Online Access:http://hdl.handle.net/10261/220637
Access Level:Open access
Keyword:Alkanes
Ruthenium tetroxide
Carbocations
Oxidations
DFT
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spelling Transient and intermediate carbocations in ruthenium tetroxide oxidation of saturated ringsPedrón, ManuelLegnani, LauraChiacchio, Maria A.Caramella, PierluigiTejero, TomásMerino, PedroAlkanesRuthenium tetroxideCarbocationsOxidationsDFTThe ruthenium tetroxide-mediated oxidation of cyclopentane, tetrahydrofuran, tetrahydrothiophene and N-substituted pyrrolidines has been studied computationally by DFT and topological (analysis of the electron localization function, ELF) methods. In agreement with experimental observations and previous DFT calculations, the rate-limiting step of the reaction takes place through a highly asynchronous (3 + 2) concerted cycloaddition through a single transition structure (one kinetic step). The ELF analysis identifies the reaction as a typical one-step-two-stages process and corroborates the existence of a transient carbocation. In the case of pyrrolidines, the carbocation is completely stabilized as an energy minimum in the form of an iminium ion and the reaction takes place in two steps.This work was supported by the Spanish Ministerio de Economía y Competitividad (MINECO) (project number CTQ2016-76155-R), by the Fondos Europeos para el Desarrollo Regional (FEDER) and the Gobierno de Aragon (Zaragoza, Spain, Groups E34-R17). The authors acknowledge the Institute of Biocomputation and Physics of Complex Systems (BIFI) at the University of Zaragoza for computer time at clusters Terminus and Memento. St. Francis-Prof. Thyagarajan Foundation (San Antonio, TX, USA) is gratefully acknowledged for a donation for software acquisition. M.-A. C. and L. L. thank Universities of Catania and Pavia for partial financial support.Peer reviewedBeilstein InstitutMinisterio de Economía y Competitividad (España)Gobierno de AragónEuropean CommissionUniversity of Texas at San AntonioUniversità degli Studi di CataniaUniversità degli studi di PaviaConsejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]202020202019info:eu-repo/semantics/articlehttp://purl.org/coar/resource_type/c_6501Publisher's versioninfo:eu-repo/semantics/publishedVersionhttp://hdl.handle.net/10261/220637reponame: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/CTQ2016-76155-Rhttps://doi.org/10.3762/bjoc.15.158Síinfo:eu-repo/semantics/openAccessoai:digital.csic.es:10261/2206372026-05-22T06:33:51Z
dc.title.none.fl_str_mv Transient and intermediate carbocations in ruthenium tetroxide oxidation of saturated rings
title Transient and intermediate carbocations in ruthenium tetroxide oxidation of saturated rings
spellingShingle Transient and intermediate carbocations in ruthenium tetroxide oxidation of saturated rings
Pedrón, Manuel
Alkanes
Ruthenium tetroxide
Carbocations
Oxidations
DFT
title_short Transient and intermediate carbocations in ruthenium tetroxide oxidation of saturated rings
title_full Transient and intermediate carbocations in ruthenium tetroxide oxidation of saturated rings
title_fullStr Transient and intermediate carbocations in ruthenium tetroxide oxidation of saturated rings
title_full_unstemmed Transient and intermediate carbocations in ruthenium tetroxide oxidation of saturated rings
title_sort Transient and intermediate carbocations in ruthenium tetroxide oxidation of saturated rings
dc.creator.none.fl_str_mv Pedrón, Manuel
Legnani, Laura
Chiacchio, Maria A.
Caramella, Pierluigi
Tejero, Tomás
Merino, Pedro
author Pedrón, Manuel
author_facet Pedrón, Manuel
Legnani, Laura
Chiacchio, Maria A.
Caramella, Pierluigi
Tejero, Tomás
Merino, Pedro
author_role author
author2 Legnani, Laura
Chiacchio, Maria A.
Caramella, Pierluigi
Tejero, Tomás
Merino, Pedro
author2_role author
author
author
author
author
dc.contributor.none.fl_str_mv Ministerio de Economía y Competitividad (España)
Gobierno de Aragón
European Commission
University of Texas at San Antonio
Università degli Studi di Catania
Università degli studi di Pavia
Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]
dc.subject.none.fl_str_mv Alkanes
Ruthenium tetroxide
Carbocations
Oxidations
DFT
topic Alkanes
Ruthenium tetroxide
Carbocations
Oxidations
DFT
description The ruthenium tetroxide-mediated oxidation of cyclopentane, tetrahydrofuran, tetrahydrothiophene and N-substituted pyrrolidines has been studied computationally by DFT and topological (analysis of the electron localization function, ELF) methods. In agreement with experimental observations and previous DFT calculations, the rate-limiting step of the reaction takes place through a highly asynchronous (3 + 2) concerted cycloaddition through a single transition structure (one kinetic step). The ELF analysis identifies the reaction as a typical one-step-two-stages process and corroborates the existence of a transient carbocation. In the case of pyrrolidines, the carbocation is completely stabilized as an energy minimum in the form of an iminium ion and the reaction takes place in two steps.
publishDate 2019
dc.date.none.fl_str_mv 2019
2020
2020
dc.type.none.fl_str_mv info:eu-repo/semantics/article
http://purl.org/coar/resource_type/c_6501
Publisher's version
info:eu-repo/semantics/publishedVersion
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/10261/220637
url http://hdl.handle.net/10261/220637
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/CTQ2016-76155-R
https://doi.org/10.3762/bjoc.15.158
Sí
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.publisher.none.fl_str_mv Beilstein Institut
publisher.none.fl_str_mv Beilstein Institut
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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