Repository logo
 
Publication

BBr3-assisted cleavage of most ethers does not follow the commonly assumed mechanism

2013Journal article Open access
Simple item page
dc.contributor.authorSilva, Carla Sousa e
dc.contributor.authorSilva, Pedro J.
dc.date.accessioned2019-09-12T09:32:29Z
dc.date.available2019-09-12T09:32:29Z
dc.date.issued2013
dc.description.abstractDensity‐functional computations were used to probe the reaction mechanism of BBr3‐assisted ether cleavage. After the initial formation of an ether–BBr3 adduct, secondary and tertiary alkyl ethers are cleaved through Br– transfer from the activated BBr3 to the alkyl moiety, as postulated in the literature. In contrast, all other ethers studied react through a novel pathway involving two ether–BBr3 adducts, one of which acts as Br– donor, and the second as the reaction substrate. The identification of the novel bimolecular mechanism for this classical reaction has further applications, because it implies that BBr3‐assisted ether cleavage may become impossible if the ether is surrounded by bulky portions of the molecule that prevent the approach of the attacking BBr3 adduct. Our data also allow the construction of an order of reactivity of alkyl ether deprotection: isopropyl, benzyl, tertiary alkyl, allyl, isobutyl and ethyl can be removed sequentially as their bromo derivatives; phenyl, cyanomethyl and chloromethyl groups can be sequentially removed as their corresponding alcohols.
dc.description.versioninfo:eu-repo/semantics/publishedVersionpt_PT
dc.identifier.citationSilva, C. Sousa e Silva, P.J. (2013). BBr3-Assisted Cleavage of Most Ethers Does Not Follow the Commonly Assumed Mechanism. European Journal of Organic Chemistry, 2013: 5195-5199. https://doi.org/10.1002/ejoc.201300337
dc.identifier.doi10.1002/ejoc.201300337pt_PT
dc.identifier.urihttp://hdl.handle.net/10284/7826
dc.language.isoengpt_PT
dc.peerreviewedyespt_PT
dc.publisherEuropean Chemical Societies Publishing
dc.relation.publisherversionhttps://doi.org/10.1002/ejoc.201300337pt_PT
dc.subjectEtherspt_PT
dc.subjectCleavage reactionspt_PT
dc.subjectReaction mechanisms
dc.subjectBoron
dc.subjectComputational chemistry
dc.titleBBr3-assisted cleavage of most ethers does not follow the commonly assumed mechanismpt_PT
dc.typejournal article
dspace.entity.typePublication
oaire.citation.endPage57pt_PT
oaire.citation.issue23pt_PT
oaire.citation.startPage1pt_PT
oaire.citation.titleEuropean Journal of Organic Chemistrypt_PT
person.familyNameSilva
person.familyNameSilva
person.givenNameCarla
person.givenNamePedro
person.identifier.ciencia-id2E1D-05DF-E0DB
person.identifier.orcid0000-0001-6467-4766
person.identifier.orcid0000-0001-9316-9275
person.identifier.ridD-8159-2013
person.identifier.scopus-author-id55310885700
rcaap.rightsopenAccesspt_PT
rcaap.typearticlept_PT
relation.isAuthorOfPublication741eff47-ffdf-4a5f-b763-3ada0062b1b8
relation.isAuthorOfPublicationf4a9230e-0a0e-45b6-b894-e71ded186ef2
relation.isAuthorOfPublication.latestForDiscovery741eff47-ffdf-4a5f-b763-3ada0062b1b8

Files

Original bundle
Now showing 1 - 1 of 1
Thumbnail Image
Name:
BBr3-assisted cleavage of most ethers does not follow the commonly assumed mechanism.pdf
Size:
1.74 MB
Format:
Adobe Portable Document Format
Download

Collections

FCS - Artigos em Revistas Científicas Internacionais com Arbitragem Científica