Repository logo
 
Publication

Influence of alkyne and azide substituents on the choice of the reaction mechanism of the Cu+-catalyzed addition of azides to iodoalkynes

2018Journal article Open access
Simple item page
dc.contributor.authorSilva, Pedro J.
dc.contributor.authorBernardo, Carlos E. P.
dc.date.accessioned2019-09-12T08:46:41Z
dc.date.available2019-09-12T08:46:41Z
dc.date.issued2018
dc.description.abstractThe cycloaddition of azides to iodoalkynes is strongly enhanced by some Cu+-complexes. We have studied computationally six reaction pathways for the cycloaddition of 24 combinations of azide and iodoalkyne to identify the dominant pathways and the influence of reactant structure on the evolution of the reaction. Two pathways were found to be operating for distinct sets of reactants. In the first pathway, initial complexation of iodoalkyne by Cu+ is followed by the binding of the azide to the metal through its substituted nitrogen atom, followed by attack of the nonhalogenated alkyne carbon by the terminal nitrogen atom. This pathway is generally followed by aromatic or electron-deficient azides, unless the iodoalkyne bears an electron-withdrawing group. The second pathway is a single-step mechanism similar (apart from the alkyne bond weakening caused by complexation) to that observed in the absence of catalyst. Electron-deficient iodoalkynes and methyl azides strongly prefer this mechanism, regardless of the identity of the reaction partners. The catalytic gain obtained through the use of Cu+ depends only partially on its direct effect on the energy of the transition state (relative to that of the infinitely separated reactants) and may be lost if the iodoalkyne itself strongly interacts with the catalyst through the formation of too strong a π-complex.pt_PT
dc.description.versioninfo:eu-repo/semantics/publishedVersionpt_PT
dc.identifier.citationSilva P.J., Bernardo C.E.P. (2018). Influence of Alkyne and Azide Substituents on the Choice of the Reaction Mechanism of the Cu+-Catalyzed Addition of Azides to Iodoalkynes. The Journal of Physical Chemistry. A,122 (37): 7497-7507. doi: 10.1021/acs.jpca.8b06894. ISSN 1089-5639.
dc.identifier.doi10.1021/acs.jpca.8b06894pt_PT
dc.identifier.eissn1520-5215
dc.identifier.issn1089-5639
dc.identifier.urihttp://hdl.handle.net/10284/7824
dc.language.isoengpt_PT
dc.peerreviewedyespt_PT
dc.relation.publisherversionhttps://dx.doi.org/10.1021/acs.jpca.8b06894pt_PT
dc.titleInfluence of alkyne and azide substituents on the choice of the reaction mechanism of the Cu+-catalyzed addition of azides to iodoalkynespt_PT
dc.typejournal article
dspace.entity.typePublication
oaire.citation.endPage7507pt_PT
oaire.citation.issue37pt_PT
oaire.citation.startPage7497pt_PT
oaire.citation.titleThe Journal of Physical Chemistry. A
oaire.citation.volume122pt_PT
person.familyNameSilva
person.givenNamePedro
person.identifier.orcid0000-0001-9316-9275
person.identifier.scopus-author-id55310885700
rcaap.rightsopenAccesspt_PT
rcaap.typearticlept_PT
relation.isAuthorOfPublicationf4a9230e-0a0e-45b6-b894-e71ded186ef2
relation.isAuthorOfPublication.latestForDiscoveryf4a9230e-0a0e-45b6-b894-e71ded186ef2

Files

Original bundle
Now showing 1 - 1 of 1
Thumbnail Image
Name:
Pre-review_The influence of alkyne and azide substituents on the choice of the reaction mechanism of the Cu+-catalyzed addition of azides to iodoalkynes.pdf
Size:
801.94 KB
Format:
Adobe Portable Document Format
Download

Collections

FCS - Artigos em Revistas Científicas Internacionais com Arbitragem Científica