Exploring the Reactivity of α-Lithiated Aryl Benzyl Ethers: Inhibition of the [1,2]-Wittig Rearrangement and the Mechanistic Proposal Revisited

By carefullycontrolling the reactiontemperature,treatment of aryl benzylethers with tBuLi selectivelyleadsto a-lithiation, generating stable organolithiums that can bedirectlytrapped with avariety of selected electro philes,before they can undergo the expected [1,2]-Wittigrear-rangement. This rearra...

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Authors: Velasco, Rocío, Silva López, Carlos, Nieto Faza, Olalla ., Sanz Díez, Roberto
Format: article
Status:Versión aceptada para publicación
Publication Date:2016
Country:España
Institution:Universidad de Burgos (UBU)
Repository:Repositorio Institucional de la Universidad de Burgos (RIUBU)
OAI Identifier:oai:riubu.ubu.es:10259/4279
Online Access:http://hdl.handle.net/10259/4279
Access Level:Open access
Keyword:density functio nal calculations
lithiation
oxygenheterocycles
reaction mechanisms
Wittig rearrangement
Chemistry, Organic
Química orgánica
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spelling Exploring the Reactivity of α-Lithiated Aryl Benzyl Ethers: Inhibition of the [1,2]-Wittig Rearrangement and the Mechanistic Proposal RevisitedVelasco, RocíoSilva López, CarlosNieto Faza, Olalla .Sanz Díez, Robertodensity functio nal calculationslithiationoxygenheterocyclesreaction mechanismsWittig rearrangementChemistry, OrganicQuímica orgánicaBy carefullycontrolling the reactiontemperature,treatment of aryl benzylethers with tBuLi selectivelyleadsto a-lithiation, generating stable organolithiums that can bedirectlytrapped with avariety of selected electro philes,before they can undergo the expected [1,2]-Wittigrear-rangement. This rearrangement has been deeplystudied,both experimentally and computationally,with aryl a-lithiat-ed benzyl ethers bearing different substituents at the arylring. The obtained resultssupport the competence of acon-certedanionic intramolecular addition/elimination sequenceand aradical dissociation/recombination sequence for ex-plaining the tendency of migrationfor aryl groups.Themore favored rearrangementsare found for substrates withelectron-poor aryl groups that favor the anionic pathwayJunta de Castilla yLejnandFEDER (BU237U13 and BU076U16) and Ministerio de Econom&ayCompetitividad (MINECO) and FEDER (CTQ2013-48937-C2-1Pand 2-P)Wiley-VCH Verlag201620172016info:eu-repo/semantics/articleinfo:eu-repo/semantics/acceptedVersionapplication/pdfhttp://hdl.handle.net/10259/4279reponame:Repositorio Institucional de la Universidad de Burgos (RIUBU)instname:Universidad de Burgos (UBU)InglésChemistry-a european journal. 2015, V. 22, n. 42, p. 15058–15068http://dx.doi.org/10.1002/chem.201602254info:eu-repo/semantics/openAccessoai:riubu.ubu.es:10259/42792026-05-28T07:56:11Z
dc.title.none.fl_str_mv Exploring the Reactivity of α-Lithiated Aryl Benzyl Ethers: Inhibition of the [1,2]-Wittig Rearrangement and the Mechanistic Proposal Revisited
title Exploring the Reactivity of α-Lithiated Aryl Benzyl Ethers: Inhibition of the [1,2]-Wittig Rearrangement and the Mechanistic Proposal Revisited
spellingShingle Exploring the Reactivity of α-Lithiated Aryl Benzyl Ethers: Inhibition of the [1,2]-Wittig Rearrangement and the Mechanistic Proposal Revisited
Velasco, Rocío
density functio nal calculations
lithiation
oxygenheterocycles
reaction mechanisms
Wittig rearrangement
Chemistry, Organic
Química orgánica
title_short Exploring the Reactivity of α-Lithiated Aryl Benzyl Ethers: Inhibition of the [1,2]-Wittig Rearrangement and the Mechanistic Proposal Revisited
title_full Exploring the Reactivity of α-Lithiated Aryl Benzyl Ethers: Inhibition of the [1,2]-Wittig Rearrangement and the Mechanistic Proposal Revisited
title_fullStr Exploring the Reactivity of α-Lithiated Aryl Benzyl Ethers: Inhibition of the [1,2]-Wittig Rearrangement and the Mechanistic Proposal Revisited
title_full_unstemmed Exploring the Reactivity of α-Lithiated Aryl Benzyl Ethers: Inhibition of the [1,2]-Wittig Rearrangement and the Mechanistic Proposal Revisited
title_sort Exploring the Reactivity of α-Lithiated Aryl Benzyl Ethers: Inhibition of the [1,2]-Wittig Rearrangement and the Mechanistic Proposal Revisited
dc.creator.none.fl_str_mv Velasco, Rocío
Silva López, Carlos
Nieto Faza, Olalla .
Sanz Díez, Roberto
author Velasco, Rocío
author_facet Velasco, Rocío
Silva López, Carlos
Nieto Faza, Olalla .
Sanz Díez, Roberto
author_role author
author2 Silva López, Carlos
Nieto Faza, Olalla .
Sanz Díez, Roberto
author2_role author
author
author
dc.subject.none.fl_str_mv density functio nal calculations
lithiation
oxygenheterocycles
reaction mechanisms
Wittig rearrangement
Chemistry, Organic
Química orgánica
topic density functio nal calculations
lithiation
oxygenheterocycles
reaction mechanisms
Wittig rearrangement
Chemistry, Organic
Química orgánica
description By carefullycontrolling the reactiontemperature,treatment of aryl benzylethers with tBuLi selectivelyleadsto a-lithiation, generating stable organolithiums that can bedirectlytrapped with avariety of selected electro philes,before they can undergo the expected [1,2]-Wittigrear-rangement. This rearrangement has been deeplystudied,both experimentally and computationally,with aryl a-lithiat-ed benzyl ethers bearing different substituents at the arylring. The obtained resultssupport the competence of acon-certedanionic intramolecular addition/elimination sequenceand aradical dissociation/recombination sequence for ex-plaining the tendency of migrationfor aryl groups.Themore favored rearrangementsare found for substrates withelectron-poor aryl groups that favor the anionic pathway
publishDate 2016
dc.date.none.fl_str_mv 2016
2016
2017
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/acceptedVersion
format article
status_str acceptedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/10259/4279
url http://hdl.handle.net/10259/4279
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv Chemistry-a european journal. 2015, V. 22, n. 42, p. 15058–15068
http://dx.doi.org/10.1002/chem.201602254
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.publisher.none.fl_str_mv Wiley-VCH Verlag
publisher.none.fl_str_mv Wiley-VCH Verlag
dc.source.none.fl_str_mv reponame:Repositorio Institucional de la Universidad de Burgos (RIUBU)
instname:Universidad de Burgos (UBU)
instname_str Universidad de Burgos (UBU)
reponame_str Repositorio Institucional de la Universidad de Burgos (RIUBU)
collection Repositorio Institucional de la Universidad de Burgos (RIUBU)
repository.name.fl_str_mv
repository.mail.fl_str_mv
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score 15,198674

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