Intramolecular Carbolithiation of 2,6-Dilithio-1,6-heptadienes: An Experimental and Theoretical Study

2,6-Dilithio-1,6-heptadienes 3 undergo intramolecular carbolithiation in Et2O/N,N,N′,N′-tetramethylethylenediamine (TMEDA) at the lithiated double bonds to afford 1,2-bis(lithiomethyl)cyclopentenes 5. Reaction of these dianions with electrophiles affords a number of 1,2-difunctionalized cyclopentene...

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Autores: Sanz, R. [0000-0003-2830-0892], Ignacio, J.M., Rodríguez, M.A. [0000-0003-0123-9905], Fañanás, F.J. [0000-0003-1947-9851], Barluenga, J. [0000-0002-6474-7782]
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2007
País:España
Institución:Universidad de La Rioja (UR)
Repositorio:RIUR. Repositorio Institucional de la Universidad de La Rioja
OAI Identifier:oai:portal.dialnet.es:doc/5bbc6829b750603269e803c4
Acceso en línea:https://investigacion.unirioja.es/documentos/5bbc6829b750603269e803c4
Access Level:acceso abierto
Palabra clave:Ab initio calculations
Carbanions
Carbolithiation
Cyclization
Cyclopentenes
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spelling Intramolecular Carbolithiation of 2,6-Dilithio-1,6-heptadienes: An Experimental and Theoretical StudySanz, R. [0000-0003-2830-0892]Ignacio, J.M.Rodríguez, M.A. [0000-0003-0123-9905]Fañanás, F.J. [0000-0003-1947-9851]Barluenga, J. [0000-0002-6474-7782]Ab initio calculationsCarbanionsCarbolithiationCyclizationCyclopentenes2,6-Dilithio-1,6-heptadienes 3 undergo intramolecular carbolithiation in Et2O/N,N,N′,N′-tetramethylethylenediamine (TMEDA) at the lithiated double bonds to afford 1,2-bis(lithiomethyl)cyclopentenes 5. Reaction of these dianions with electrophiles affords a number of 1,2-difunctionalized cyclopentene derivatives 7-10. The ease of carbolithiation of 2,6-dilithio-1,6-heptadiene (3a) compared to that of 2-lithio-1,6-heptadiene (14) has been studied experimentally. A series of ab initio molecular-orbital calculations on the course of the reaction were carried out and the results were compared to those for the corresponding intramolecular carbolithiation of an isolated double bond. The Li-C interactions found in the transition state by this theoretical study support a carbolithiation pathway for the cyclization of 2,6-dilithio-1,6-heptadienes. © 2007 Wiley-VCH Verlag GmbH & Co. KGaA.2007info:eu-repo/semantics/articleSubtype: Articleinfo:eu-repo/semantics/publishedVersionapplication/pdfhttps://investigacion.unirioja.es/documentos/5bbc6829b750603269e803c4reponame:RIUR. Repositorio Institucional de la Universidad de La Riojainstname:Universidad de La Rioja (UR)Inglésinfo:eu-repo/semantics/altIdentifier/doi/10.1002/CHEM.200601863info:eu-repo/semantics/altIdentifier/wos/WOS:000247219900029info:eu-repo/semantics/altIdentifier/pissn/0947-6539Intramolecular Carbolithiation of 2,6-Dilithio-1,6-heptadienes: An Experimental and Theoretical Study, 2007, vol. 13, núm. 17, pág. 4998-5008info:eu-repo/semantics/openAccessoai:portal.dialnet.es:doc/5bbc6829b750603269e803c42026-06-14T12:47:17Z
dc.title.none.fl_str_mv Intramolecular Carbolithiation of 2,6-Dilithio-1,6-heptadienes: An Experimental and Theoretical Study
title Intramolecular Carbolithiation of 2,6-Dilithio-1,6-heptadienes: An Experimental and Theoretical Study
spellingShingle Intramolecular Carbolithiation of 2,6-Dilithio-1,6-heptadienes: An Experimental and Theoretical Study
Sanz, R. [0000-0003-2830-0892]
Ab initio calculations
Carbanions
Carbolithiation
Cyclization
Cyclopentenes
title_short Intramolecular Carbolithiation of 2,6-Dilithio-1,6-heptadienes: An Experimental and Theoretical Study
title_full Intramolecular Carbolithiation of 2,6-Dilithio-1,6-heptadienes: An Experimental and Theoretical Study
title_fullStr Intramolecular Carbolithiation of 2,6-Dilithio-1,6-heptadienes: An Experimental and Theoretical Study
title_full_unstemmed Intramolecular Carbolithiation of 2,6-Dilithio-1,6-heptadienes: An Experimental and Theoretical Study
title_sort Intramolecular Carbolithiation of 2,6-Dilithio-1,6-heptadienes: An Experimental and Theoretical Study
dc.creator.none.fl_str_mv Sanz, R. [0000-0003-2830-0892]
Ignacio, J.M.
Rodríguez, M.A. [0000-0003-0123-9905]
Fañanás, F.J. [0000-0003-1947-9851]
Barluenga, J. [0000-0002-6474-7782]
author Sanz, R. [0000-0003-2830-0892]
author_facet Sanz, R. [0000-0003-2830-0892]
Ignacio, J.M.
Rodríguez, M.A. [0000-0003-0123-9905]
Fañanás, F.J. [0000-0003-1947-9851]
Barluenga, J. [0000-0002-6474-7782]
author_role author
author2 Ignacio, J.M.
Rodríguez, M.A. [0000-0003-0123-9905]
Fañanás, F.J. [0000-0003-1947-9851]
Barluenga, J. [0000-0002-6474-7782]
author2_role author
author
author
author
dc.subject.none.fl_str_mv Ab initio calculations
Carbanions
Carbolithiation
Cyclization
Cyclopentenes
topic Ab initio calculations
Carbanions
Carbolithiation
Cyclization
Cyclopentenes
description 2,6-Dilithio-1,6-heptadienes 3 undergo intramolecular carbolithiation in Et2O/N,N,N′,N′-tetramethylethylenediamine (TMEDA) at the lithiated double bonds to afford 1,2-bis(lithiomethyl)cyclopentenes 5. Reaction of these dianions with electrophiles affords a number of 1,2-difunctionalized cyclopentene derivatives 7-10. The ease of carbolithiation of 2,6-dilithio-1,6-heptadiene (3a) compared to that of 2-lithio-1,6-heptadiene (14) has been studied experimentally. A series of ab initio molecular-orbital calculations on the course of the reaction were carried out and the results were compared to those for the corresponding intramolecular carbolithiation of an isolated double bond. The Li-C interactions found in the transition state by this theoretical study support a carbolithiation pathway for the cyclization of 2,6-dilithio-1,6-heptadienes. © 2007 Wiley-VCH Verlag GmbH & Co. KGaA.
publishDate 2007
dc.date.none.fl_str_mv 2007
dc.type.none.fl_str_mv info:eu-repo/semantics/article
Subtype: Article
info:eu-repo/semantics/publishedVersion
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv https://investigacion.unirioja.es/documentos/5bbc6829b750603269e803c4
url https://investigacion.unirioja.es/documentos/5bbc6829b750603269e803c4
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1002/CHEM.200601863
info:eu-repo/semantics/altIdentifier/wos/WOS:000247219900029
info:eu-repo/semantics/altIdentifier/pissn/0947-6539
Intramolecular Carbolithiation of 2,6-Dilithio-1,6-heptadienes: An Experimental and Theoretical Study, 2007, vol. 13, núm. 17, pág. 4998-5008
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.source.none.fl_str_mv reponame:RIUR. Repositorio Institucional de la Universidad de La Rioja
instname:Universidad de La Rioja (UR)
instname_str Universidad de La Rioja (UR)
reponame_str RIUR. Repositorio Institucional de la Universidad de La Rioja
collection RIUR. Repositorio Institucional de la Universidad de La Rioja
repository.name.fl_str_mv
repository.mail.fl_str_mv
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